Adhesive for temporary bonding, adhesive layer, wafer work piece and method for manufacturing semiconductor device using same, rework solvent, polyimide copolymer, polyimide mixed resin, and resin composition (as amended)

ABSTRACT

The present invention provides a temporary-bonding adhesive having excellent heat resistance, whereby a semiconductor circuit formation substrate and a support substrate can be bonded by a single type of adhesive layer, the adhesive force thereof does not change over the course of steps for manufacturing a semiconductor device or the like, and the adhesive can subsequently be easily de-bonded at room temperature under mild conditions; and a method for manufacturing a semiconductor device using the temporary-bonding adhesive. The present invention includes a temporary-bonding adhesive wherein a polyimide copolymer having at least an acid dianhydride residue and a diamine residue, the diamine residue including both of (A1) a polysiloxane-based diamine residue represented by a general formula (1) in which n is a natural number from 1 to 15, and (B1) a polysiloxane-based diamine residue represented by a general formula (1) in which n is a natural number from 16 to 100, the polyimide copolymer containing 40-99.99 mol % of the (A1) residue and 0.01-60 mol % of the (B1) residue.

CROSS REFERENCE TO RELATED APPLICATIONS

This is the U. S. National Phase application of PCT InternationalApplication No. PCT/JP2015/072248, filed Aug. 5, 2015, and claimspriority to Japanese Patent Application No. 2014-162145, filed Aug. 8,2014, and Japanese Patent Application No. 2014-200265, filed Sep. 30,2014, the disclosures of each of these applications being incorporatedherein by reference in their entireties for all purposes.

FIELD OF THE INVENTION

The present invention relates to a temporary-bonding adhesive, anadhesive layer, a wafer work piece and a method for manufacturing asemiconductor device using the same, a rework solvent, a polyimidecopolymer, a polyimide mixed resin, and a resin composition.

BACKGROUND OF THE INVENTION

In recent years, reductions of weight and thickness of semiconductordevices are proceeding. Technical development in which a semiconductorchip is laminated while being connected through TSV (through-siliconvia) in order to achieve higher levels of integration and greaterpackaging density of the semiconductor device, are being pursued.Further, in the field of power semiconductors, a reduction of conductionloss is required for saving of energy. In order to solve such problems,it is necessary to reduce a thickness of package, and it is investigatedto reduce a thickness of a semiconductor circuit formation substrate toat least 1 μm and at most 100 μm and to process the semiconductorcircuit formation substrate. In this step, a surface where a circuit isnot formed (backside) of the semiconductor circuit formation substrateis polished to reduce a thickness, and a back electrode is formed on thebackside. In order to prevent fractures of the semiconductor circuitformation substrate during the steps of polishing and the like, thesemiconductor circuit formation substrate is fixed to a supportsubstrate having supporting properties, such as a silicon wafer or aglass substrate, to form a wafer work piece, the wafer work piece issubjected to polishing and back-circuit formation processing, and thenthe processed semiconductor circuit formation substrate is de-bonded offfrom the support substrate. In order to bond the semiconductor circuitformation substrate to the support substrate, a temporary-bondingadhesive is used as an adhesive layer. This manufacturing methodsometimes includes a step of reworking an adhesive layer or a residue ofan adhesive layer respectively remaining on the semiconductor circuitformation substrate or the support substrate with an organic solvent, analkaline aqueous solution or the like after the step of de-bonding offthe semiconductor circuit formation substrate from the supportsubstrate. The organic solvent, the alkaline aqueous solution or thelike is referred to as a rework solvent.

Herein, heat resistance enough to endure a semiconductor step isrequired of the temporary-bonding adhesive, and it is required of thetemporary-bonding adhesive that the semiconductor circuit formationsubstrate can be easily de-bonded off after completion of the processingstep. As such a temporary-bonding adhesive, for example, an adhesive inwhich a polyamide-based or polyimide-based adhesive layer respectivelyhaving heat resistance is used, and an adhesive force is varied byheating, and thereby the semiconductor circuit formation substrate isde-bonded off (e.g., refer to Patent Document 1), is proposed. Further,a wafer work piece having a constitution including two types of adhesivelayers of a thermoplastic organo polysiloxane-based adhesive layerhaving heat resistance and a curable modified siloxane-based adhesivelayer, wherein these adhesive layers have an adhesive force againstwhich each of the semiconductor circuit formation substrate and thesupport substrate can be de-bonded off and is de-bonded off bymechanically applying a force at room temperature, is proposed (e.g.,Patent Document 2). Further, one which is composed of a single type ofcycloolefin-based adhesive layer, and is de-bonded off by mechanicallyapplying a force at room temperature, is proposed (e.g., Patent Document3).

PATENT DOCUMENTS

-   Patent Document 1: Japanese Patent Laid-open Publication No.    2010-254808 (CLAIMS)-   Patent Document 2: Japanese Patent Laid-open Publication No.    2013-48215 (CLAIMS)-   Patent Document 3: Japanese Patent Laid-open Publication No.    2013-241568 (CLAIMS)

SUMMARY OF THE INVENTION

However, the temporary-bonding adhesive in which de-bonding can beperformed only by heating like Patent Document 1 has problems that asolder bump is melted during a heating step for de-bonding, and anadhesive force during a processing step is deteriorated to cause thesemiconductor to de-bond off in the middle of the step, or an adhesiveforce during a processing step is increased to cause the semiconductornot to de-bond off.

The temporary-bonding adhesive like Patent Document 2 in whichde-bonding off is performed by mechanically applying a force at roomtemperature does not have the above-mentioned problems. However, twotypes of adhesive layers need to be formed, and there is a problem ofputting a sizable load on the process. The temporary-bonding adhesivelike Patent Document 3 is one in which de-bonding off is performed bymechanically applying a force at room temperature by a single type ofadhesive layer. However, a cycloolefin-based material has a problem thematerial is decomposed in the semiconductor step underhigh-temperatures.

In view of such situations, it is an object of the present invention toprovide a temporary-bonding adhesive which can bond a semiconductorcircuit formation substrate and a support substrate to each other by asingle type of adhesive, has excellent heat resistance and thereby doesnot undergo a change in the adhesive force over the course of steps formanufacturing a semiconductor device or the like, and can subsequentlybe easily de-bonded by applying a mechanical force or dissolving in arework solvent at room temperature under mild conditions; an adhesivelayer; a wafer work piece and a method for manufacturing a semiconductordevice using the wafer work piece; a rework solvent; a polyimidecopolymer; a polyimide mixed resin; and a resin composition.

That is, the present invention includes a temporary-bonding adhesive,wherein the temporary-bonding adhesive is a polyimide copolymer havingat least an acid dianhydride residue and a diamine residue, the diamineresidue includes both of (A1) a polysiloxane-based diamine residuerepresented by a general formula (1) in which n is a natural number of 1to 15, and (B1) a polysiloxane-based diamine residue represented by ageneral formula (1) in which n is a natural number of 16 to 100, and thepolyimide copolymer contains 40 to 99.99 mol % of the (A1) residue and0.01 to 60 mol % of the (B1) residue:

in which n is a natural number, R¹ and R² may be the same or differentand represent an alkylene group having 1 to 30 carbon atoms or aphenylene group, and R³ to R⁶ may be the same or different and representan alkyl group having 1 to 30 carbon atoms, a phenyl group, or a phenoxygroup.

Further, the present invention includes a temporary-bonding adhesive,wherein the temporary-bonding adhesive is a polyimide mixed resinincluding (A2) a polyimide and/or a precursor thereof containing apolysiloxane-based diamine residue represented by a general formula (1)in which n is a natural, number of 1 to 15 and not containing apolysiloxane-based diamine residue represented by a general formula (1)in which n is a natural number of 16 to 100, and (B2) a polyimide and/ora precursor thereof containing a polysiloxane-based diamine residuerepresented by a general formula (1) in which n is a natural number of16 to 100 and not containing a polysiloxane-based diamine residuerepresented by a general formula (1) in which n is a natural number of 1to 15, and the polyimide mixed resin contains 40 to 99.99 wt % of the(A2) and 0.01 to 60 wt % of the (B2).

in which n is a natural number, R¹ and R² may be the same or differentand represent an alkylene group having 1 to 30 carbon atoms or aphenylene group, and R³ to R⁶ may be the same or different and representan alkyl group having 1 to 30 carbon atoms, a phenyl group, or a phenoxygroup.

Further, the present invention includes a temporary-bonding adhesive,wherein the temporary-bonding adhesive is a resin composition containing(a) a resin (excluding a siloxane polymer represented by a generalformula (2)), and at least one of (b-1) a siloxane polymer representedby a general formula (2) and (b-2) a compound represented by a generalformula (3):

in which m is an integer of 10 to 100, R⁷ and R⁸ may be the same ordifferent and represent a monovalent organic group having 1 to 30 carbonatoms and 0 to 3 nitrogen atoms, R⁹ and R¹⁰ may be the same or differentand represent an alkylene group having 1 to 30 carbon atoms or aphenylene group, and R¹¹ to R¹⁴ may be the same or different andrepresent an alkyl group having 1 to 30 carbon atoms, an alkylene grouphaving 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbonatoms, a phenyl group, or a phenoxy group.

in which R¹⁵ represents a monovalent organic group having 2 to 20 carbonatoms and 1 to 3 nitrogen atoms, R¹⁶ represents hydrogen, an alkyl grouphaving 1 to 20 carbon atoms, or an aromatic group, and a represents aninteger of 0 to 4.

Further, the present invention includes an adhesive layer obtained byforming a coating of the temporary-bonding adhesive according to anaspect of the present invention.

Further, the present invention includes a wafer work piece formed bybonding a semiconductor circuit lamination substrate to a supportsubstrate with at least the adhesive layer according to an aspect of thepresent invention interposed therebetween.

Further, the present invention includes a method for manufacturing asemiconductor device using the wafer work piece according to an aspectof the present invention including at least any one of a step offabricating the semiconductor circuit formation substrate into a thinnerone, a step of subjecting the semiconductor circuit formation substrateof the wafer work piece to device processing, a step of de-bonding offthe semiconductor circuit formation substrate of the wafer work piecefrom a support substrate, and a step of washing, with a solvent, anadhesive layer adhering to the semiconductor circuit formation substratede-bonded off from the wafer work piece or the support substrate of thewafer work piece.

Further, the present invention includes a rework solvent for cleaningthe adhesive layer adhering to the de-bonded semiconductor circuitformation substrate or support substrate, wherein the rework solventcontains at least (A) an amine-based solvent and (B) a solventrepresented by the general formula (6):

in which R²⁵ and R²⁶ independently represent hydrogen, alkyl groupshaving 1 to 12 carbon atoms, an acetyl group, or aromatic groups, R²⁷represents hydrogen or a methyl group, b is either 0, 1 or 2, and c isan integer of 1 to 3.

Further, the present invention includes a polyimide copolymer having atleast an acid dianhydride residue and a diamine residue, wherein thediamine residue includes both of (A1) a polysiloxane-based diamineresidue represented by a general formula (1) in which n is a naturalnumber of 1 to 15, and (B1) a polysiloxane-based diamine residuerepresented by a general formula (1) in which n is a natural number of16 to 100, and the polyimide copolymer contains 40 to 99.99 mol % of the(A1) residue and 0.01 to 60 mol % of the (B1) residue:

in which n is a natural number, R¹ and R² may be the same or differentand represent an alkylene group having 1 to 30 carbon atoms or aphenylene group, and R³ to R⁶ may be the same or different and representan alkyl group having 1 to 30 carbon atoms, a phenyl group, or a phenoxygroup.

Further, the present invention includes a polyimide mixed resinincluding (A2) a polyimide and/or a precursor thereof having at least anacid dianhydride residue and a diamine residue, containing apolysiloxane-based diamine residue represented by a general formula (1)in which n is a natural number of 1 to 15 and not containing apolysiloxane-based diamine residue represented by a general formula (1)in which n is a natural number of 16 to 100, and (B2) a polyimide and/ora precursor thereof having at least an acid dianhydride residue and adiamine residue, containing a polysiloxane-based diamine residuerepresented by a general formula (1) in which n is a natural number of16 to 100 and not containing a polysiloxane-based diamine residuerepresented by a general formula (1) in which n is a natural number of 1to 15, and the polyimide mixed resin contains 40 to 99.99 wt % of the(A2) and 0.01 to 60 wt % of the (B2):

in which n is a natural number, R¹ and R² may be the same or differentand represent an alkylene group having 1 to 30 carbon atoms or aphenylene group, and R³ to R⁶ may be the same or different and representan alkyl group having 1 to 30 carbon atoms, a phenyl group, or a phenoxygroup.

Further, the present invention includes a resin composition containing(a) a resin (excluding a siloxane polymer represented by a generalformula (2)), and at least one of (b-1) a siloxane polymer representedby a general formula (2) and (b-2) a compound represented by a generalformula (3), wherein the (a) resin is a polyimide resin having at leastan acid dianhydride residue and a diamine residue and including, in thediamine residue, a polysiloxane-based diamine residue represented by ageneral formula (5) which is 40 mol % or more in all diamine residues.

in which m is an integer of 10 to 100, R⁷ and R⁸ may be the same ordifferent and represent a monovalent organic group having 1 to 30 carbonatoms and 0 to 3 nitrogen atoms, R⁹ and R¹⁰ may be the same or differentand represent an alkylene group having 1 to 30 carbon atoms or aphenylene group, and R¹¹ to R¹⁴ may be the same or different andrepresent an alkyl group having 1 to 30 carbon atoms, an alkylene grouphaving 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbonatoms, a phenyl group, or a phenoxy group.

in which R¹⁵ represents a monovalent organic group having 2 to 20 carbonatoms and 1 to 3 nitrogen atoms, R¹⁸ represents hydrogen, an alkyl grouphaving 1 to 20 carbon atoms, or an aromatic group, and a represents aninteger of 0 to 4.

in which L is an integer of 1 to 100, R¹⁹ and R²⁰ may be the same ordifferent and represent an alkylene group having 1 to 30 carbon atoms ora phenylene group, and R²¹ to R²⁴ may be the same or different andrepresent an alkyl group having 1 to 30 carbon atoms, a phenyl group, ora phenoxy group.

According to the present invention, it is possible to provide atemporary-bonding adhesive having excellent heat resistance which canbond a semiconductor circuit formation substrate and a support substrateto each other by a single type of adhesive, has excellent heatresistance and thereby does not undergo a change in the adhesive forceover the course of steps for manufacturing a semiconductor device or thelike, and can subsequently be easily de-bonded by applying a mechanicalforce or dissolving in a rework solvent at room temperature under mildconditions; an adhesive layer; a wafer work piece and a method formanufacturing a semiconductor device using the wafer work piece; arework solvent; a polyimide copolymer; a polyimide mixed resin; and aresin composition.

DETAILED DESCRIPTION OF EMBODIMENTS OF THE INVENTION

A temporary-bonding adhesive according to an aspect of the presentinvention is a polyimide copolymer which has at least an aciddianhydride residue and a diamine residue, wherein the diamine residueincludes both of (A1) a polysiloxane-based diamine residue representedby a general formula (1) in which n is a natural number of 1 to 15 and(B1) a polysiloxane-based diamine residue represented by a generalformula (1) in which n is a natural number of 16 to 100:

in which n is a natural number, R¹ and R² may be the same or differentand represent an alkylene group having 1 to 30 carbon atoms or aphenylene group, and R³ to R⁶ may be the same or different and representan alkyl group having 1 to 30 carbon atoms, a phenyl group, or a phenoxygroup.

The polyimide copolymer of the present invention can be prepared byusing at least (A1) a polysiloxane-based diamine represented by thegeneral formula (1) in which n is a natural number of 1 to 15 and (B1) apolysiloxane-based diamine represented by the general formula (1) inwhich n is a natural number of 16 to 100 as diamine components in thepolymerization of a polyimide, and copolymerizing the (A1) with the(B1). By containing two types or more of polysiloxane-based diamines inwhich natural numbers n are different, the adhesiveness of the surfaceof the adhesive layer can be lowered in the step of forming the adhesivelayer on the substrate serving as an adherend, and therefore it ispossible that the semiconductor circuit formation substrate and thesupport substrate are bonded to each other and then the semiconductorcircuit formation substrate and the support substrate are de-bonded offfrom each other by mechanically applying a force at room temperatureunder a mild condition. Further, the semiconductor circuit formationsubstrate and the support substrate can also be de-bonded off from eachother by dissolving the adhesive layer under a mild condition of roomtemperature using a rework solvent described later or the like.

The polyimide copolymer according to an aspect of the present inventioncontains, in all diamine residues, 40 to 99.99 mol % of the (A1)polysiloxane-based diamine residue represented by the general formula(1) in which n is a natural number of 1 to 15. By containing 40 to 99.99wt % of the (A1) polysiloxane-based diamine residue represented by thegeneral formula (1) in which n is a natural number of 1 to 15, thepolyimide copolymer can exhibit high adhesiveness and can bond asemiconductor circuit formation substrate to a support substrate.

Further, the polyimide copolymer according to an aspect of the presentinvention contains 0.01 to 60 mol % of the (B1) polysiloxane-baseddiamine residue represented by the general formula (1) in which n is anatural number of 16 to 100. The content of the (B1) is more preferably0.01 to 30 mol %. By containing 0.01 to 60 mol % of the (B1)polysiloxane-based diamine residue represented by the general formula(1) in which n is a natural number of 16 to 100, it is possible toprevent voids from being generated in the adhesive layer during a stepof processing a device after bonding a semiconductor circuit formationsubstrate to a support substrate. Moreover, when the content of the (B1)residue is 0.01 to 30 wt %, it is more preferred since the voids are notgenerated in the adhesive layer during the step of processing a deviceand high heat resistance can be exhibited.

The polyimide copolymer of the present invention may be a polyimideprecursor which is cyclized by heating to become a polyimide, or may bea polyimide which has been cyclized by heating, or may be a polyimideprecursor a part of which has been cyclized by heating.

The temporary-bonding adhesive of the present invention includes apolyimide mixed resin including (A2) a polyimide and/or a precursorthereof containing a polysiloxane-based diamine residue represented by ageneral formula (1) in which n is a natural number of 1 to 15 and notcontaining a polysiloxane-based diamine residue represented by a generalformula (1) in which n is a natural number of 16 to 100, and (B2) apolyimide and/or a precursor thereof containing a polysiloxane-baseddiamine residue represented by a general formula (1) in which n is anatural number of 16 to 100 and not containing a polysiloxane-baseddiamine residue represented by a general formula (1) in which n is anatural number of 1 to 15:

in which n is a natural number, R¹ and R² may be the same or differentand represent an alkylene group having 1 to 30 carbon atoms or aphenylene group, and R³ to R⁶ may be the same or different and representan alkyl group having 1 to 30 carbon atoms, a phenyl group, or a phenoxygroup.

The polyimide mixed resin of the present invention can be prepared bymixing a polymerization solution or a powder of (A2) a polyimide and/ora precursor thereof containing a polysiloxane-based diamine residuerepresented by a general formula (1) in which n is a natural number of 1to 15 and not containing a polysiloxane-based diamine residuerepresented by a general formula (1) in which n is a natural number of16 to 100 with a polymerization solution or a powder of (B2) a polyimideand/or a precursor thereof containing a polysiloxane-based diamineresidue represented by a general formula (1) in which n is a naturalnumber of 16 to 100 and not containing a polysiloxane-based diamineresidue represented by a general formula (1) in which n is a naturalnumber of 1 to 15.

By mixing the (A2) polyimide and/or the precursor thereof and the (B2)polyimide and/or the precursor thereof

which respectively contain polysiloxane-based diamine residues havingdifferent polymerization degrees n, the adhesiveness of the surface ofthe adhesive layer can be lowered in the step of forming the adhesivelayer on the substrate serving as an adherend, and therefore it ispossible that the semiconductor circuit formation substrate and thesupport substrate are bonded to each other and then the semiconductorcircuit formation substrate and the support substrate are de-bonded offfrom each other by mechanically applying a force at room temperatureunder a mild condition. Further, the semiconductor circuit formationsubstrate and the support substrate can also be de-bonded off from eachother by dissolving the adhesive layer under a mild condition of roomtemperature using a rework solvent described later or the like.

The polyimide mixed resin according to an aspect of the presentinvention contains 40 to 99. 99 wt % of the (A2) polyimide and/or theprecursor thereof containing a polysiloxane-based diamine residuerepresented by a general formula (1) in which n is a natural number of 1to 15 and not containing a polysiloxane-based diamine residuerepresented by a general formula (1) in which n is a natural number of16 to 100. By containing 40 to 99.99 wt % of the (A2), the polyimidemixed resin can exhibit high adhesiveness and can bond a semiconductorcircuit formation substrate to a support substrate.

Further, the polyimide mixed resin according to an aspect of the presentinvention contains 0.01 to 60 wt % of the (B2) polyimide and/or theprecursor thereof containing a polysiloxane-based diamine residuerepresented by a general formula (1) in which n is a natural number of16 to 100 and not containing a polysiloxane-based diamine residuerepresented by a general formula (1) in which n is a natural number of 1to 15. The content of the (B2) is more preferably 0.01 to 30 wt %. Bycontaining 0.01 to 60 wt % of the (B2), it is possible to prevent voidsfrom being generated in the adhesive layer during a step of processing adevice after bonding a semiconductor circuit formation substrate to asupport substrate. Moreover, when the content of the (B2) is 0.01 to 30wt %, it is more preferred since the voids are not generated in theadhesive layer and high heat resistance can be exhibited.

An average molecular weight of the polysiloxane-based diamine can bedetermined by calculating an amino group equivalent by performingneutralization titration of an amino group of polysiloxane-based diamineand doubling the amino group equivalent. For example, a predeterminedamount of polysiloxane-based diamine serving as a specimen is taken andput into a beaker, and the polysiloxane-based diamine is dissolved in apredetermined amount of a mixed solution of isopropyl alcohol(hereinafter, referred to as IPA) and toluene in proportions of 1:1. Tothe resulting solution, a 0.1 N aqueous hydrochloric acid solution isadded dropwise while stirring the solution, an amount of the 0.1 Naqueous hydrochloric acid solution added dropwise until reaching aneutralization point is determined, and thereby, the amino groupequivalent can be calculated. A value obtained by doubling the aminogroup equivalent is the average molecular weight.

On the other hand, a molecular weight of the polysiloxane-based diamineused is calculated from its chemical structural formula for the cases ofn=1 and n=10, and thereby, a relationship between the value of n and themolecular weight can be obtained as a relational expression of a linearfunction. By applying the above average molecular weight to therelational expression, an average value of the above n can bedetermined.

Further, since there may be cases where the polysiloxane-based diaminerepresented by the general formula (1) is a mixture where n is not asingle value but a plurality of n exists, n represents an average valuein the invention.

Specific examples of the polysiloxane-based diamine represented by thegeneral formula (1) include α,ω-bis(3-aminopropyl)polydimethylsiloxane,α,ω-bis(3-aminopropyl)polydiethylsiloxane,α,ω-bis(3-aminopropyl)polydipropylsiloxane,α,ω-bis(3-aminopropyl)polydibutylsiloxane,α,ω-bis(3-aminopropyl)polydiphenoxysiloxane,α,ω-bis(2-aminoethyl)polydimethylsiloxane,α,ω-bis(2-aminoethyl)polydiphenoxysiloxane,α,ω-bis(4-aminobutyl)polydimethylsiloxane,α,ω-bis(4-aminobutyl)polydiphenoxysiloxane,α,ω-bis(5-aminopentyl)polydimethylsiloxane,α,ω-bis(5-aminopentyl)polydiphenoxysiloxane,α,ω-bis(4-aminophenyl)polydimethylsiloxane,α,ω-bis(4-aminophenyl)polydiphenoxysiloxane, and the like. Thepolysiloxane-based diamines described above may be used singly, or twoor more species thereof may be used.

Polyimide constituting the polyimide copolymer and the polyimide mixedresin of the present invention may have a residue of aromatic diamine ora residue of alicyclic diamine. The content of the residue of thearomatic diamine or the residue of the alicyclic diamine is preferably0.1 mol % or more and 40 mol % or less in all diamine residues.

Specific examples of the residue of the aromatic diamine or thealicyclic diamine include 2,5-diaminophenol, 3,5-diaminophenol,3,3′-dihydroxybenzidine, 4,4′-dihydroxy-3,3′-diaminophenyl propane,4,4′-dihydroxy-3,3′-diaminophenyl hexafluoropropane,4,4′-dihydroxy-3,3′-diaminophenyl sulfone,4,4′-dihydroxy-3,3′-diaminophenyl ether,3,3′-dihydroxy-4,4′-diaminophenyl ether,4,4′-dihydroxy-3,3′-diaminophenyl propane methane,4,4′-dihydroxy-3,3′-diaminobenzophenone, 1,3-bis(4-amino-3-hydroxyphenylbenzene, 1,3-bis(3-amino-4-hydroxy phenyl)benzene,bis(4-(4-amino-3-hydroxy phenoxy)benzene)propane,bis(4-(3-amino-4-hydroxy phenoxy)benzene)sulfone,bis(4-(3-amino-4-hydroxy phenoxy)biphenyl, p-phenylene diamine,m-phenylene diamine, 2,5-diaminotoluene, 2,4-diaminotoluene,3,5-diaminobenzoic acid, 2,6-diaminobenzoic acid,2-methoxy-1,4-phenylene diamine, 4,4′-diaminobenzanilide,3,4′-diaminobenzanilide, 3,3′-diaminobenzanilide,3,3′-dimethyl-4,4′-diaminobenzanilide, 9,9-bis(4-aminophenyl)fluorene,9,9-bis(3-aminophenyl)fluorene, 9,9-bis(3-methyl-4-aminophenyl)fluorene,9,9-bis(3,5-dimethyl-4-aminophenyl)fluorene,9,9-bis(3-methoxy-4-aminophenyl)fluorene,9,9-bis(4-aminophenyl)fluorene-4-carboxylic acid,9,9-bis(4-aminophenyl)fluorene-4-methyl,9,9-bis(4-aminophenyl)fluorene-4-methoxy,9,9-bis(4-aminophenyl)fluorene-4-ethyl,9,9-bis(4-aminophenyl)fluorene-4-sulfone,9,9-bis(4-aminophenyl)fluorene-3-carboxylic acid,9,9-bis(4-aminophenyl)fluorene-3-methyl, 1,3-diaminocyclohexane,2,2′-dimethyl benzidine, 3,3′-dimethyl benzidine, 3,3′-dimethoxybenzidine, 2,4-diaminopyridine, 2,6-diaminopyridine,1,5-diaminonaphthalene, 2,7-diaminofluorene, p-amino benzylamine,m-amino benzylamine, 4,4′-bis(4-aminophenoxy)biphenyl,4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether,3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl sulfone,3,3′-diaminodiphenyl sulfone, 3,3′-diaminodiphenyl methane,4,4′-diaminodiphenyl methane, 4,4′-diaminodiphenyl sulfide, 3,3′-diaminobenzophenone, 3,4′-diamino benzophenone, 4,4′-diamino benzophenone,3,3′-dimethyl-4,4′-diaminodiphenyl methane,1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene,1,4-bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene,2,2-bis[4-(4-aminophenoxyl)phenyl]propane,2,2-bis[4-(3-aminophenoxyl)phenyl]propane,bis[4-(4-aminophenoxyl)phenyl]methane,bis[4-(3-aminophenoxyl)phenyl]methane,bis[4-(4-aminophenoxyl)phenyl]ether,bis[4-(3-aminophenoxyl)phenyl]ether,bis[4-(4-aminophenoxyl)phenyl]sulfone,bis[4-(3-aminophenoxyl)phenyl]sulfone,2,2-bis[4-(4-aminophenoxyl)phenyl]hexafluoropropane, 1,4-diaminocyclohexane, 4,4′-methylene bis (cyclohexyl amine), 3,3′-methylenebis(cyclohexyl amine), 4,4′-diamino-3,3′-dimethyl dicyclohexyl methane,4,4′-diamino-3,3′-dimethyl dicyclohexyl, benzidine, and the like. Thearomatic diamines or the alicyclic diamines described above may be usedsingly, or two or more species thereof may be used.

Among these aromatic diamines and alicyclic diamines, aromatic diamineswith a structure having high bendability are preferred, andspecifically,

1,3-bis(3-aminophenoxy)benzene, 3,3′-diaminodiphenyl sulfone,4,4′-diaminodiphenylether, 3,3′-diaminodiphenylether, and3,3′-diaminobenzophenone are particularly preferred.

Among the aromatic diamines and alicyclic diamines, the aromaticdiamines represented by a general formula (4) are preferably contained.When containing the aromatic diamines represented by a general formula(4), compatibility between the inorganic particles and the polyimidecopolymer or the polyimide mixed resin described later can be improved,to suppress the sedimentation of inorganic particles:

in which R¹⁷ and R¹⁸ may be the same or different and represent groupsselected from among an alkyl group having 1 to 30 carbon atoms, analkoxy group having 1 to 30 carbon atoms, a fluoroalkyl group having 1to 30 carbon atoms, a hydroxyl group, halogen, a carboxyl group, acarboxylate ester group, a phenyl group, a sulfone group, a nitro groupand a cyano group, and X represents a direct bond or the following bondstructure.

The halogen referred to herein refers to fluorine, chlorine, bromine, oriodine.

The content of the aromatic diamine represented by the general formula(4) is preferably 0.1 mol % or more and 40 mol % or less, and morepreferably 0.1 mol % or more and 30 mol % or less in all diamineresidues.

Polyimide constituting the polyimide copolymer and the polyimide mixedresin of the present invention preferably includes the residue of anaromatic tetracarboxylic dianhydride as the residue of the aciddianhydride. Specific examples of the aromatic tetracarboxylicdianhydride include pyromellitic dianhydride,3,3′,4,4′-biphenyltetracarboxylic dianhydride,2,2′-dimethyl-3,3′,4,4′-biphenyltetracarboxylic dianhydride,5,5′-dimethyl-3,3′,4,4′-biphenyltetracarboxylic dianhydride,2,3,3′,4′-biphenyltetracarboxylic dianhydride,2,2′,3,3″-biphenyltetracarboxylic dianhydride, 3,3′,4,4′-diphenyl ethertetracarboxylic dianhydride, 2,3,3′,4′-diphenyl ether tetracarboxylicdianhydride, 2,2′,3,3′-diphenyl ether tetracarboxylic dianhydride,3,3′,4,4′-benzophenone tetracarboxylic dianhydride,2,2′,3,3′-benzophenone tetracarboxylic dianhydride,2,3,3′,4′-benzophenone tetracarboxylic dianhydride,3,3′,4,4′-diphenylsulfone tetracarboxylic dianhydride,2,3,3′,4′-diphenylsulfone tetracarboxylic dianhydride,3,3′,4,4′-diphenylsulfoxide tetracarboxylic dianhydride,3,3′,4,4′-diphenylsulfide tetracarboxylic dianhydride,3,3′,4,4′-diphenylmethylene tetracarboxylic dianhydride,4,4′-isopropylidenediphthalic anhydride,4,4′-(hexafluoroisopropylidene)diphthalic anhydride,3,4,9,10-perylenetetracarboxylic dianhydride,2,3,6,7-naphthalenetetracarboxylic dianhydride,1,4,5,8-naphthalenetetracarboxylic dianhydride,1,2,5,6-naphthalenetetracarboxylic dianhydride,3,3″,4,4″-p-terphenyltetracarboxylic dianhydride,3,3″,4,4″-m-terphenyltetracarboxylic dianhydride,2,3,6,7-anthracenetetracarboxylic dianhydride,1,2,7,8-phenanethrenetetracarboxylic dianhydride, and the like. Theabove-mentioned aromatic tetracarboxylic dianhydrides may be usedsingly, or two or more species thereof may be used.

Further, in the present invention, the residue of a tetracarboxylicdianhydride having an aliphatic ring can be contained in the polyimideconstituting the polyimide copolymer and the polyimide mixed resin tosuch an extent that the heat resistance of the polyimide copolymer andthe polyimide mixed resin is not impaired. Specific examples of thetetracarboxylic dianhydride having an aliphatic ring include2,3,5-tricarboxycyclopentyl acetic dianhydride,1,2,3,4-cyclobutanetetracarboxylic dianhydride,1,2,3,4-cyclopentanetetracarboxylic dianhydride,1,2,3,5-cyclopentanetetracarboxylic dianhydride,1,2,4,5-bicyclohexenetetracarboxylic dianhydride,1,2,4,5-cyclohexanetetracarboxylic dianhydride, and 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C]furane-1,3-dione. The above-mentioned tetracarboxylic dianhydrides maybe used singly, or two or more species thereof may be used.

A molecular weight of the polyimide constituting the polyimide copolymerand the polyimide mixed resin of the present invention can be adjustedby making a tetracarboxylic acid component and a diamine component to berespectively used for synthesis equal in the number of moles to eachother or by making either of these components excessive. It is alsopossible to make either of the tetracarboxylic acid component or thediamine component excessive and block a terminal of a polymer chain witha terminal blocking agent such as an acid component or an aminecomponent. As the terminal blocking agent of the acid component,dicarboxylic acid or an anhydride thereof is preferably used, and as theterminal blocking agent of the amine component, monoamine is preferablyused. In doing so, it is preferred that an acid equivalent of thetetracarboxylic acid component and an amine equivalent of the diaminecomponent are equal in the number of moles to each other includingterminal blocking agent of the acid component or the amine component.

When a mole ratio is adjusted so that the tetracarboxylic acid componentis excessive or the diamine component is excessive, dicarboxylic acidsuch as benzoic acid, phthalic anhydride, tetrachlorophthalic anhydrideand aniline or anhydrides thereof, or monoamine may be added as aterminal blocking agent.

In the present invention, a molar ratio of the tetracarboxylic acidcomponent to the diamine component in the polyimide copolymer and thepolyimide mixed resin can be appropriately adjusted so as to have aviscosity range of the resin composition to facilitate use of the resincomposition in coating, and the molar ratio of the tetracarboxylic acidcomponent to the diamine component is generally adjusted to the range of100/100 to 100/95 or 100/100 to 95/100. If lacking a molar balance, amolecular weight of a resin is decreased, mechanical strength of aformed film is decreased, and an adhesive force tends to become low, andtherefore it is preferred to adjust the molar ratio to such an extentthat the adhesive force does not become low.

A polymerization method of the polyimide constituting the polyimidecopolymer and the polyimide mixed resin of the present invention is notparticularly limited. For example, when polymerization of polyamic acidserving as a polyimide precursor is performed, tetracarboxylicdianhydride and diamine are stirred at a temperature of 0 to 100° C. for1 to 100 hours in an organic solvent to obtain a polyamic acid resinsolution. When the polyimide resin is soluble in the organic solvent,after the polymerization of the polyamic acid, the polyamic acid isstirred as-is for 1 to 100 hours raising a temperature thereof to 120 to300° C., and thereby the polyamic acid is converted to polyimide toobtain a polyimide resin solution. In this time, toluene, o-xylene,m-xylene or p-xylene may be added to a reaction solution to remove waterto be produced by an imidization reaction by azeotropy of these solventand water.

Further, the present invention includes a temporary-bonding adhesive,wherein the temporary-bonding adhesive is a resin composition containing(a) a resin (excluding a siloxane polymer represented by a generalformula (2)), and at least one of (b-1) a siloxane polymer representedby a general formula (2) and (b-2) a compound represented by a generalformula (3).

A type of the (a) resin (excluding a siloxane polymer including astructure represented by a general formula (2)) is not particularlylimited, and any one which is generally usable for electronic materialapplications may be used. The reason for this is that as describedlater, when the resin composition contains at least one of (b-1) asiloxane polymer represented by a general formula (2) and (b-2) acompound represented by a general formula (3), heat resistance can beimproved.

Examples of the (a) resin include, but not limited to, polymer resinssuch as polyimide-based resins, acrylic resins, acrylonitrile-basedresins, butadiene-based resins, urethane-based resins, polyester-basedresins, polyamide-based resins, polyamide-imide-based resins,epoxy-based resins, phenolic resins, silicone-based resins, andalicyclic resins. These resins may be used singly, or may be used incombination of two or more thereof.

The glass transition temperature of the (a) resin is preferably 100° C.or lower. When the glass transition temperature is 100° C. or lower, theadhesive can exhibit high tackiness when a substrate serving as anadherend is thermocompression bonded to an adhesive layer of thetemporary-bonding adhesive of the present invention.

Further, a 1% weight Loss temperature of the (a) resin is preferably300° C. or higher, and more preferably 350° C. or higher. When the 1%weight Loss temperature is 300° C. or higher, the voids are notgenerated in the adhesive layer during the step of processing a deviceand high heat resistance can be exhibited. The 1% weight Losstemperature of the present invention can be measured with use of athermogravimetric analyzer (TGA). Measuring methods will be specificallydescribed. A predetermined amount of a resin is put in TGA and held at60° C. for 30 minutes to remove a water content which the resin hasabsorbed. Then, a temperature of the resin is raised at a rate of 5°C./min to 500° C. In the resulting weight Loss curve, a temperature atwhich a weight of the resin is decreased by 1% is determined and definedas a 1% weight Loss temperature.

The (a) resin of the present invention is preferably a polyimide resin.When the (a) resin is a polyimide resin, it can be easily achieved thatthe glass transition temperature is 100° C. or lower and that the 1%weight Loss temperature is 300° C. or higher.

The above-mentioned polyimide resin has at least an acid dianhydrideresidue and a diamine residue, and preferably includes apolysiloxane-based diamine residue represented by the general formula(5) in the diamine residue.

in which L is an integer of 1 to 100, R¹⁹ and R²⁰ may be the same ordifferent and represent an alkylene group having 1 to 30 carbon atoms ora phenylene group, and R²¹ to R²⁴ may be the same or different andrepresent an alkyl group having 1 to 30 carbon atoms, a phenyl group, ora phenoxy group.

An average molecular weight of the polysiloxane-based diamine can bedetermined by calculating an amino group equivalent by performingneutralization titration of an amino group of polysiloxane-based diamineand doubling the amino group equivalent. For example, a predeterminedamount of polysiloxane-based diamine serving as a specimen is taken andput into a beaker, and the polysiloxane-based diamine is dissolved in apredetermined amount of a mixed solution of isopropyl alcohol(hereinafter, referred to as IPA) and toluene in proportions of 1:1. Tothe resulting solution, a 0.1 N aqueous hydrochloric acid solution isadded dropwise while stirring the solution, an amount of the 0.1 Naqueous hydrochloric acid solution added dropwise until reaching aneutralization point is determined, and thereby, the amino groupequivalent can be calculated. A value obtained by doubling the aminogroup equivalent is the average molecular weight.

On the other hand, a molecular weight of the polysiloxane-based diamineused is calculated from its chemical structural formula for the cases ofL=1 and L=10, and thereby, a relationship between the value of n and themolecular weight can be obtained as a relational expression of a linearfunction. By applying the above average molecular weight to therelational expression, an average value of the above n can bedetermined.

Further, since there may be cases where the polysiloxane-based diaminerepresented by the general formula (5) is a mixture where L is not asingle value but a plurality of n exists, L represents an average valuein the invention.

Specific examples of the polysiloxane-based diamine represented by thegeneral formula (5) include α,ω-bis(3-aminopropyl)polydimethylsiloxane,α,ω-bis(3-aminopropyl)polydiethylsiloxane,α,ω-bis(3-aminopropyl)polydipropylsiloxane,α,ω-bis(3-aminopropyl)polydibutylsiloxane,α,ω-bis(3-aminopropyl)polydiphenoxysiloxane,α,ω-bis(2-aminoethyl)polydimethylsiloxane,α,ω-bis(2-aminoethyl)polydiphenoxysiloxane,α,ω-bis(4-aminobutyl)polydimethylsiloxane,α,ω-bis(4-aminobutyl)polydiphenoxysiloxane,α,ω-bis(5-aminopentyl)polydimethylsiloxane,α,ω-bis(5-aminopentyl)polydiphenoxysiloxane,α,ω-bis(4-aminophenyl)polydimethylsiloxane,α,ω-bis(4-aminophenyl)polydiphenoxysiloxane, and the like. Thepolysiloxane-based diamines described above may be used singly, or twoor more species thereof may be used. Among these polysiloxane-baseddiamines, polysiloxane-based diamines in which n is 2 or more arepreferred, and such diamines can lower a glass transition temperature ofa resin. The glass transition temperature of a resin is preferably 100°C. or lower, and the adhesive can exhibit high adhesiveness whenthermocompression bonding.

The content of the residue of the polysiloxane-based diamine representedby the general formula (5) is preferably 30 mol % or more, and morepreferably 40 mol % or more in all diamine residues. Because the residueof the polysiloxane-based diamine is in the above range, a glasstransition temperature of the resin can be significantly lowered.

The polyimide resin may have the residue of aromatic diamine or theresidue of alicyclic diamine. The content of the residue of the aromaticdiamine or the residue of the alicyclic diamine is preferably 0.1 mol %or more and 70 mol % or less, and more preferably 0.1 mol % or more and60 mol % or less in all diamine residues.

Specific examples of the aromatic diamine or the alicyclic diamineinclude 2,5-diaminophenol, 3,5-diaminophenol, 3,3′-dihydroxybenzidine,4,4′-dihydroxy-3,3′-diaminophenyl propane,4,4′-dihydroxy-3,3′-diaminophenyl hexafluoropropane,4,4′-dihydroxy-3,3′-diaminophenyl sulfone,4,4′-dihydroxy-3,3′-diaminophenyl ether,3,3′-dihydroxy-4,4′-diaminophenyl ether,4,4′-dihydroxy-3,3′-diaminophenyl propane methane,4,4′-dihydroxy-3,3′-diaminobenzophenone, 1,3-bis(4-amino-3-hydroxyphenyl)benzene, 1,3-bis(3-amino-4-hydroxy phenyl)benzene,bis(4-(4-amino-3-hydroxy phenoxy)benzene)propane,bis(4-(3-amino-4-hydroxy phenoxy)benzene)sulfone,bis(4-(3-amino-4-hydroxy phenoxy))biphenyl, p-phenylene diamine,m-phenylene diamine, 2,5-diaminotoluene, 2,4-diaminotoluene,3,5-diaminobenzoic acid, 2,6-diaminobenzoic acid,2-methoxy-1,4-phenylene diamine, 4,4′-diaminobenzanilide,3,4′-diaminobenzanilide, 3,3′-diaminobenzanilide,3,3′-dimethyl-4,4′-diaminobenzanilide, 9,9-bis(4-aminophenyl)fluorene,9,9-bis(3-aminophenyl)fluorene, 9,9-bis(3-methyl-4-aminophenyl)fluorene,9,9-bis(3,5-dimethyl-4-aminophenyl)fluorene,9,9-bis(3-methoxy-4-aminophenyl)fluorene,9,9-bis(4-aminophenyl)fluorene-4-carboxylic acid,9,9-bis(4-aminophenyl)fluorene-4-methyl,9,9-bis(4-aminophenyl)fluorene-4-methoxy,9,9-bis(4-aminophenyl)fluorene-4-ethyl,9,9-bis(4-aminophenyl)fluorene-4-sulfone,9,9-bis(4-aminophenyl)fluorene-3-carboxylic acid,9,9-bis(4-aminophenyl)fluorene-3-methyl, 1,3-diaminocyclohexane,2,2′-dimethyl benzidine, 3,3′-dimethyl benzidine, 3,3′-dimethoxybenzidine, 2,4-diaminopyridine, 2,6-diaminopyridine,1,5-diaminonaphthalene, 2,7-diaminofluorene, p-amino benzylamine,m-amino benzylamine, 4,4′-bis(4-aminophenoxy)biphenyl,4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether,3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl sulfone,3,3′-diaminodiphenyl sulfone, 3,3′-diaminodiphenyl methane,4,4′-diaminodiphenyl methane, 4,4′-diaminodiphenyl sulfide, 3,3′-diaminobenzophenone, 3,4′-diamino benzophenone, 4,4′-diamino benzophenone,3,3′-dimethyl-4,4′-diaminodiphenyl methane,1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene,1,4-bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene,2,2-bis[4-(4-aminophenoxyl)phenyl]propane,2,2-bis[4-(3-aminophenoxyl)phenyl]propane,bis[4-(4-aminophenoxyl)phenyl]methane,bis[4-(3-aminophenoxyl)phenyl]methane,bis[4-(4-aminophenoxyl)phenyl]ether,bis[4-(3-aminophenoxyl)phenyl]ether,bis[4-(4-aminophenoxyl)phenyl]sulfone,bis[4-(3-aminophenoxyl)phenyl]sulfone,2,2-bis[4-(4-aminophenoxyl)phenyl]hexafluoropropane, 1,4-diaminocyclohexane, 4,4′-methylene bis(cyclohexyl amine), 3,3′-methylenebis(cyclohexyl amine), 4,4′-diamino-3,3′-dimethyl dicyclohexyl methane,4,4′-diamino-3,3′-dimethyl dicyclohexyl, benzidine, and the like. Thearomatic diamines or the alicyclic diamines described above may be usedsingly, or two or more species thereof may be used.

Among these aromatic diamines and alicyclic diamines, aromatic diamineswith a structure having high bendability are preferred, andspecifically, 1,3-bis(3-aminophenoxy)benzene, 3,3′-diaminodiphenylsulfone, 4,4′-diaminodiphenylether, 3,3′-diaminodiphenylether, and3,3′-diaminobenzophenone are particularly preferred.

Among the aromatic diamines and alicyclic diamines, the aromaticdiamines represented by a general formula (4) are preferably contained.When containing the aromatic diamines represented by a general formula(4), compatibility between the inorganic particles and the polyimidecopolymer or the polyimide mixed resin described later can be improvedto suppress the sedimentation of inorganic particles:

in which R¹⁷ and R¹⁸ may be the same or different and represent groupsselected from among an alkyl group having 1 to 30 carbon atoms, analkoxy group having 1 to 30 carbon atoms, a fluoroalkyl group having 1to 30 carbon atoms, a hydroxyl group, halogen, a carboxyl group, acarboxylate ester group, a phenyl group, a sulfone group, a nitro groupand a cyano group, and X represents a direct bond or the following bondstructure.

The halogen referred to herein refers to fluorine, chlorine, bromine, oriodine.

The content of the aromatic diamine represented by the general formula(4) is preferably 0.1 mol % or more and 40 mol % or less, and morepreferably 0.1 mol % or more and 30 mol % or less in all diamineresidues.

The above-mentioned polyimide resin preferably includes the residue ofan aromatic tetracarboxylic dianhydride as the residue of the aciddianhydride. When the polyimide resin includes the residue of anaromatic tetracarboxylic dianhydride, the 1% weight Loss temperature is300° C. or higher, and therefore the voids are not generated in theadhesive layer during the step of processing a device and high heatresistance can be exhibited.

Specific examples of the aromatic tetracarboxylic dianhydride includepyromellitic dianhydride, 3,3′,4,4′-biphenyltetracarboxylic dianhydride,2,2′-dimethyl-3,3′,4,4′-biphenyltetracarboxylic dianhydride,5,5′-dimethyl-3,3′,4,4′-biphenyltetracarboxylic dianhydride,2,3,3′,4′-biphenyltetracarboxylic dianhydride,2,2′,3,3′-biphenyltetracarboxylic dianhydride, 3,3′,4,4′-diphenyl ethertetracarboxylic dianhydride, 2,3,3′,4′-diphenyl ether tetracarboxylicdianhydride, 2,2′,3,3′-diphenyl ether tetracarboxylic dianhydride,3,3′,4,4′-benzophenone tetracarboxylic dianhydride,2,2′,3,3′-benzophenone tetracarboxylic dianhydride,2,3,3′,4′-benzophenone tetracarboxylic dianhydride,3,3′,4,4′-diphenylsulfone tetracarboxylic dianhydride,2,3,3′,4′-diphenylsulfone tetracarboxylic dianhydride,3,3′,4,4′-diphenylsulfoxide tetracarboxylic dianhydride,3,3′,4,4′-diphenylsulfide tetracarboxylic dianhydride,3,3′,4,4′-diphenylmethylene tetracarboxylic dianhydride,4,4′-isopropylidenediphthalic anhydride,4,4′-(hexafluoroisopropylidene)diphthalic anhydride,3,4,9,10-perylenetetracarboxylic dianhydride,2,3,6,7-naphthalenecarboxylic dianhydride,1,4,5,8-naphthalenetetracarboxylic dianhydride,1,2,5,6-naphthalenetetracarboxylic dianhydride,3,3″,4,4″-p-terphenyltetracarboxylic dianhydride,3,3″,4,4″-m-terphenyltetracarboxylic dianhydride,2,3,6,7-anthracenetetracarboxylic dianhydride,1,2,7,8-phenanethrenetetracarboxylic dianhydride, and the like. Theabove-mentioned aromatic tetracarboxylic dianhydrides may be usedsingly, or two or more species thereof may be used.

Further, a tetracarboxylic dianhydride having an aliphatic ring can becontained to such an extent that the heat resistance of the polyimideresin is not impaired. Specific examples of the tetracarboxylicdianhydride having an aliphatic ring include 2,3,5-tricarboxycyclopentylacetic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride,1,2,3,4-cyclopentanetetracarboxylic dianhydride,1,2,3,5-cyclopentanetetracarboxylic dianhydride,1,2,4,5-bicyclohexenetetracarboxylic dianhydride,1,2,4,5-cyclohexanetetracarboxylic dianhydride, and1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C]furane-1,3-dione.The above-mentioned tetracarboxylic dianhydrides may be used singly, ortwo or more species thereof may be used.

A molecular weight of the polyimide resin can be adjusted by making atetracarboxylic acid component and a diamine component to berespectively used for synthesis equal in the number of moles to eachother or by making either of these components excessive. It is alsopossible to make either of the tetracarboxylic acid component or thediamine component excessive and block a terminal of a polymer chain witha terminal blocking agent such as an acid component or an aminecomponent. As the terminal blocking agent of the acid component,dicarboxylic acid or an anhydride thereof is preferably used, and as theterminal blocking agent of the amine component, monoamine is preferablyused. In doing so, it is preferred that an acid equivalent of thetetracarboxylic acid component and an amine equivalent of the diaminecomponent are equal in the number of moles to each other includingterminal blocking agent of the acid component or the amine component.

When a mole ratio is adjusted so that the tetracarboxylic acid componentis excessive or the diamine component is excessive, dicarboxylic acidsuch as benzoic acid, phthalic anhydride, tetrachlorophthalic anhydrideand aniline or anhydrides thereof, or monoamine may be added as aterminal blocking agent.

A molar ratio of the tetracarboxylic acid component to the diaminecomponent in the polyimide resin can be appropriately adjusted so as tohave a viscosity range of the resin composition to facilitate use of theresin composition in coating, and the molar ratio of the tetracarboxylicacid component to the diamine component is generally adjusted to therange of 100/100 to 100/95 or 100/100 to 95/100. If lacking a molarbalance, a molecular weight of a resin is decreased, mechanical strengthof a formed film is decreased, and an adhesive force tends to becomelow, and therefore it is preferred to adjust the molar ratio to such anextent that the adhesive force does not become low.

A polymerization method of the polyimide resin of the present inventionis not particularly limited. For example, when polymerization ofpolyamic acid serving as a polyimide precursor is performed,tetracarboxylic dianhydride and diamine are stirred at a temperature of0 to 100° C. for 1 to 100 hours in an organic solvent to obtain apolyamic acid resin solution. When the polyimide resin is soluble in theorganic solvent, after the polymerization of the polyamic acid, thepolyamic acid is stirred as-is for 1 to 100 hours raising a temperaturethereof to 120 to 300° C., and thereby the polyamic acid is converted topolyimide to obtain a polyimide resin solution. In this time, toluene,o-xylene, m-xylene or p-xylene may be added to a reaction solution toremove water to be produced by an imidization reaction by azeotropy ofthese solvent and water.

The polyimide resin may be a polyimide, or may be a polyamic acid whichis a precursor of the polyimide. The polyimide resin may be a polyimideprecursor a part of which is cyclized and imidized.

The (b-1) siloxane polymer represented by a general formula (2) will bedescribed.

in which m is an integer of 10 to 100, R⁷ and R⁸ may be the same ordifferent and represent a monovalent organic group having 0 to 3nitrogen atoms, R⁹ and R¹⁰ may be the same or different and represent analkylene group having 1 to 30 carbon atoms or a phenylene group, and R¹¹to R¹⁴ may be the same or different and represent an alkyl group having1 to 30 carbon atoms, an alkylene group having 1 to 30 carbon atoms, analkoxy group having 1 to 30 carbon atoms, a phenyl group, or a phenoxygroup.

In addition, the alkoxy group having 1 to 30 carbon atoms does notinclude a polyoxyalkylene structure.

R⁷ and R⁸ may be the same or different and represent a monovalentorganic group having 1 to 30 carbon atoms and 0 to 3 nitrogen atoms. Forexample, structures having an alkyl group, an alkylene group, an alkoxygroup, a phenyl group, a phenoxy group, an amino group, a carboxylgroup, a hydroxyl group, an epoxy group, an oxetane group, an ethergroup, an aralkyl group, an amide group, an imide group, a nitro groupor an ester group, can be used.

In the general formula (2), m is an integer of 10 to 100. By containingthe siloxane polymer in which m is 10 to 100, the adhesiveness of thesurface of the adhesive layer obtained by applying a resin compositiononto a wafer and drying the resin composition can be lowered, andtherefore it is possible that the semiconductor circuit formationsubstrate and the support substrate are bonded to each other and thenthe semiconductor circuit formation substrate and the support substrateare de-bonded off from each other by mechanically applying a force atroom temperature under a mild condition. Further, the semiconductorcircuit formation substrate and the support substrate can also bede-bonded off from each other by dissolving the adhesive layer under amild condition of room temperature using a rework solvent describedlater or the like.

Further, by containing the siloxane polymer in which m is 10 to 100,heat resistance of the surface of the adhesive layer can be improved, itis possible to prevent voids from being generated in the adhesive layerduring a step of processing a device after bonding a semiconductorcircuit formation substrate to a support substrate.

From the viewpoint of heat resistance, R⁷ and R⁸ are preferably astructure having an aromatic ring or aromatic heterocyclic structure.When the R⁷ and the R⁸ are a structure having an aromatic ring oraromatic heterocyclic structure, it is possible to more prevent voidsfrom being generated in the adhesive layer during a step of processing adevice after bonding a semiconductor circuit formation substrate to asupport substrate. Specific examples of the R⁷ and R⁸ include thefollowing structures, but are not limited to these structures.

The content of the (b-1) siloxane polymer represented by the generalformula (2) is preferably 0.01 to 30 wt % with respect to the (a) resin.The content is more preferably 0.1 wt % or more and 15 wt % or less. Bysetting the content to 0.01 wt %, releasability and heat resistance canbe improved, and by setting the content to 30 wt % or less, adhesivenessbetween the adhesive layer and the support substrate can be maintained.Further, the (b-1) siloxane polymer represented by the general formula(2) may be added during the polymerization of the (a) resin, or may beadded after the polymerization of the (a) resin.

The (b-2) compounds represented by the general formula (3) will bedescribed.

in which R¹⁵ represents a monovalent organic group having 2 to 20 carbonatoms and 1 to 3 nitrogen atoms, R¹⁶ represents hydrogen, an alkyl grouphaving 1 to 20 carbon atoms, or an aromatic group, and a represents aninteger of 0 to 4.

By containing the (b-2) compound represented by the general formula (3),the adhesiveness between the adhesive layer and the support substratecan be improved, and therefore heat resistance can be improved, it ispossible to prevent voids from being generated in the adhesive layerduring a step of processing a device after bonding a semiconductorcircuit formation substrate to a support substrate.

When the adhesive layer does not contain the (b-1) siloxane polymerrepresented by the general formula (2) and contains only the (b-2)compound represented by the general formula (3), the adhesiveness of thesurface of the adhesive layer is intensive, and the semiconductorcircuit formation substrate is hardly de-bonded by applying a mechanicalforce. However, the semiconductor circuit formation substrate can bede-bonded by dissolving the adhesive layer under a mild condition ofroom temperature using a rework solvent described later and the like.

R¹⁵ represents a monovalent organic group having 2 to 20 carbon atomsand 1 to 3 nitrogen atoms. As such an organic group, for example, astructure having an amino group, an isocyanate group, or a ureide groupcan be used. Specific examples of the compound represented by thegeneral formula (3) include the following structures, but are notlimited to these structures.

Further, from the viewpoint of heat resistance, R¹⁵ is preferably astructure having an aromatic ring or aromatic heterocyclic structure.Preferred specific examples of the compound represented by the generalformula (3) include the following structures, but are not limited thesestructures.

The content of the (b-2) compound represented by the general formula (3)is preferably 0.01 to 30 wt % with respect to the (a) resin. The contentis more preferably 0.1 wt % or more and 15 wt % or less. When thecontent of the compound is set to 0.1 wt %, there is an effect of moresuppressing generation of the voids, and when the content is set to 15wt % or less, an increase in flowability of the adhesive layer issuppressed, and consequently, generation of the voids in the adhesivelayer during the step of processing a device, can be more suppressed.Further, the (b-2) compound represented by the general formula (3) maybe added during the polymerization of the (a) resin, or may be addedafter the polymerization of the (a) resin.

The temporary-bonding adhesive of the present invention may contain asolvent. Solvents, for example, polar aprotic solvents such asN-methyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide,N,N-dimethylacetamide, and dimethyl sulfoxide; ethers such astetrahydrofuran, dioxane, and propylene glycol monomethyl ether; ketonessuch as acetone, methyl ethyl ketone, and diisobutyl ketone; esters suchas ethyl acetate, propylene glycol monomethyl ether acetate, and ethyllactate; and aromatic hydrocarbons such as toluene, and xylene, may beused singly, or two or more species thereof may be used.

An SP value of the solvent contained in the temporary-bonding adhesiveof the present invention is preferably 7.5 to 9.0. The SP value is morepreferably 7.5 to 8.0. When the polyimide resin is used for thepolyimide copolymer, the polyimide mixed resin, or the (a) resin, sincethe polyimide resin contains a low polar polysiloxane-based diamineresidue and a residue including a high polar imide group and a highpolar aromatic group, the storage stability is poor and the resincomposition tends to cause phase separation. However, by containing asolvent in which the SP value is 7.5 to 9.0, the phase separation of theresin composition does not occur and good storage stability can beexhibited.

Examples of the solvent having the SP value of 7.5 to 9.0 include methylacetate (SP value; 8.8), ethyl acetate (SP value; 8.7), 3-methoxybutylacetate (SP value; 8.7), diethylene glycol methyl ethyl ether (SP value;8.2), diethylene glycol dimethyl ether (SP value; 8.1), dipropyleneglycol methyl ether acetate (SP value; 8.7), methyl ethyl ketone (SPvalue; 9.0), dipropylene glycol dimethyl ether (SP value; 7.8),dipropylene glycol methyl-n-propyl ether (SP value; 8.0), and the like.These solvents may be used singly, or two or more species thereof may beused.

There are various methods concerning how to determine the SP value of asolvent. In the present specification, an SP value calculated from anestimation method proposed by Fedors will be used. In the Fedors method,total cohesion energy and a total molar volume of a whole substance arecalculated from cohesion energy and a molar volume of a structural unitof a substance, and the square root of a value obtained by dividing thetotal cohesion energy by the total molar volume is take as an SP value.

A solvent represented by the general formula (6) is preferred from theviewpoint of the solubility of the polyimide resin used for thepolyimide copolymer, the polyimide mixed resin, or the (a) resin.

in which R²⁵ and R²⁶ independently represent hydrogen, alkyl groupshaving 1 to 12 carbon atoms, an acetyl group, or aromatic groups, R²⁷represents hydrogen or a methyl group, b is either 0, 1 or 2, and c isan integer of 1 to 3.

Specific examples of the solvents represented by the general formula (6)include, but not limited to, propylene glycol mono-t-butyl ether,ethylene glycol mono-t-butyl ether, propylene glycol mono-n-butyl ether,propylene glycol monopropyl ether, propylene glycol monoethyl ether,ethylene glycol mono-n-butyl ether, ethylene glycol monopropyl ether,dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether,dipropylene glycol dipropyl ether, dipropylene glycol di-n-butyl ether,dipropylene glycol di-t-butyl ether, dipropylene glycol monomethylether, dipropylene glycol monoethyl ether, dipropylene glycol monopropylether, dipropylene glycol mono-n-butyl ether, tripropylene glycolmonomethyl ether, tripropylene glycol monoethyl ether, tripropyleneglycol monopropyl ether, diethylene glycol methyl ethyl ether, anddiethylene glycol dimethyl ether.

As the solvent contained in the temporary-bonding adhesive of thepresent invention, solvents which are represented by the general formula(6) and have the SP value of 7.5 to 9.0, are more preferred. Examples ofsuch solvents include dipropylene glycol dimethyl ether (SP value; 7.8),dipropylene glycol methyl-n-propyl ether (SP value; 8.0), diethyleneglycol methyl ethyl ether (SP value; 8.2), diethylene glycol dimethylether (SP value; 8.1), and the like. Dipropylene glycol dimethyl ether(SP value; 7.8) and dipropylene glycol methyl-n-propyl ether (SP value;8.0), in which the SP values are 7.5 to 8.0, are more preferred.

Further, other solvents may be added to such an extent that the effectsof the storage stability and solubility of the polyimide copolymer, thepolyimide mixed resin or the (a) resin is not impaired. Examples thereofinclude, but not limited to, amide-based polar solvents such asN-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide,and 1,3-dimethyl-2-imidazoline; lactone-based polar solvents such asβ-propiolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone,γ-caprolactone, and ε-caprolactone; and ethyl lactate and the like.

In the polymerization method of the siloxane polyimide resin describedabove, it is also possible to leave the organic solvent, which has beenused as a polymerization solvent, as a solvent contained in thetemporary-bonding adhesive without being removed from a polymerizationsolution.

The temporary-bonding adhesive of the present invention preferablycontains inorganic particles. By containing the inorganic particles, theheat resistance of the resin composition can be improved. Specificexamples of a material of the inorganic particles include silica,alumina, titanium oxide, quartz powder, magnesium carbonate, potassiumcarbonate, barium sulfate, mica, talc and the like. Further, theinorganic particles may be added during the polymerization of thepolyimide copolymer, the polyimide mixed resin, or the (a) resin, or maybe added after the polymerization.

The content of the inorganic particles is preferably 0.1 wt % or moreand 40 wt % or less with respect to the polyimide copolymer, thepolyimide mixed resin, or the (a) resin. The content is more preferably0.1 wt % or more and 20 wt % or less.

When the polyimide resin used for the polyimide copolymer, the polyimidemixed resin, or the (a) resin, is a polyamic acid resin, the polyamicacid resin is applied onto a substrate such as a wafer or glass anddried to form a coated film, and then the polyamic acid resin isconverted to polyimide by a heat treatment. A temperature of 240° C. orhigher is required for conversion from the polyimide precursor to thepolyimide. However, when an imidization catalyst is contained in thetemporary-bonding adhesive, imidization becomes possible at a lowertemperature and in a shorter time. Specific examples of the imidizationcatalyst include, but not limited to, pyridine, trimethylpyridine,β-picoline, quinoline, isoquinoline, imidazole, 2-methylimidazole,1,2-dimethylimidazole, 2-phenylimidazole, 2,6-lutidine, triethylamine,m-hydroxybenzoic acid, 2,4-dihydroxybenzoic acid, p-hydroxyphenylaceticacid, 4-hydroxyphenylpropionic acid, p-phenolsulfonic acid,p-aminophenol, p-aminobenzoic acid and the like.

The content of the imidization catalyst is preferably 3 wt % or more,and more preferably 5 wt % or more with respect to 100 wt % of thepolyimide copolymer, the polyimide mixed resin, or the polyimide resin.When containing the imidization catalyst in an amount of 3 wt % or more,imidization can be completed even by a heat treatment at lowertemperature. Further, the content of the imidization catalyst ispreferably 10 wt % or less, and more preferably 8 wt % or less. Bysetting the content of the imidization catalyst to 10 wt % or less, itis possible to minimize an amount of the imidization catalyst whichremains in a polyimide-based resin layer after the heat treatment tosuppress generation of volatile portions. Further, the imidizationcatalyst may be added during the polymerization of the polyimidecopolymer, the polyimide mixed resin, or the (a) resin, or may be addedafter the polymerization.

Other resins may be added to the temporary-bonding adhesive of thepresent invention to such an extent that the effect of the presentinvention is not impaired. Further, a surfactant, a silane couplingagent or the like may be added for the purpose of improvingcharacteristics such as tackiness, heat resistance, coating properties,and storage stability. Further, other resins, the surfactant or thesilane coupling agent may be added during the polymerization of thepolyimide copolymer, the polyimide mixed resin, or the (a) resin, or maybe added after the polymerization.

The temporary-bonding adhesive of the present invention can be used formanufacturing of a semiconductor device. Specifically, thetemporary-bonding adhesive can be used for manufacturing of asemiconductor device which includes the step of reducing a thickness ofthe semiconductor circuit formation substrate to at least 1 μm and atmost 100 μm. Examples thereof include manufacturing of a semiconductordevice in which a semiconductor chip is laminated while being connectedthrough TSV (through-silicon via) in order to achieve higher levels ofintegration and greater packaging density of the semiconductor device. Asilicon substrate is generally used for the semiconductor circuitformation substrate.

When the thickness of the silicon substrate is reduced to at least 1 μmand at most 100 μm, since it is difficult to carry the siliconsubstrate, a semiconductor circuit formation substrate is bonded to asupport substrate such as a silicon substrate or a glass substrate usinga temporary-bonding adhesive to prepare a wafer work piece. A surfacewhere a circuit is not formed (backside) of the semiconductor circuitformation substrate of the wafer work piece is polished to reduce athickness, and thereafter the semiconductor circuit formation substrateis subjected to device processing. Thereafter, the semiconductor circuitformation substrate is de-bonded off from the support substrate. Thetemporary-bonding adhesive of the present invention can be suitably usedas an adhesive in manufacturing of a semiconductor device including anyone of the above-mentioned steps.

Examples of applying the temporary-bonding adhesive onto the supportsubstrate include spin coating, roll coating, screen printing, slit diecoating, and the like. By continuously or intermittently heat-treatingthe temporary-bonding adhesive at 180 to 450° C. for 1 to 3 hours afterapplying the adhesive and drying it at 100 to 150° C., an adhesive layerhaving excellent adhesiveness and excellent heat resistance can beprepared. Further, using a laminated film formed by applying thetemporary-bonding adhesive onto a base film subjected to releasetreatment, drying and laminating the adhesive, an applied film of thetemporary-bonding adhesive may be transferred to a silicon substrate orglass substrate serving as a support substrate to be laminated thereon.When the temporary-bonding adhesive is further heat-treated at 180 to450° C. for 1 to 3 hours after lamination of the temporary-bondingadhesive, an adhesive layer having excellent adhesiveness and excellentheat resistance can be prepared.

In the present invention, the temporary-bonding adhesive may be not onlyapplied onto the support substrate to be laminated thereon, but alsoapplied onto the semiconductor circuit formation substrate to belaminated thereon, or using the laminated film, the applied film of thetemporary-bonding adhesive may be transferred to the semiconductorcircuit formation substrate to be laminated thereon. Further, a layermade of another resin composition may be present on a support substrateside or semiconductor circuit formation substrate side of the adhesivelayer.

Examples of methods of de-bonding off the semiconductor circuitformation substrate include a thermal slide off method, a laser lift offmethod, a mechanical de-bonding method at room temperature, a solventrelease method at room temperature and the like. The temporary-bondingadhesive of the present invention can be suitably used in the mechanicalde-bonding method at room temperature or the solvent release method atroom temperature. The mechanical de-bonding method at room temperatureis a method in which the semiconductor circuit formation substrate isgradually de-bonded off from an end of the substrate in a mechanical wayat room temperature. The solvent release method at room temperature is amethod in which the support substrate has been provided with holes forasolvent passage in advance, and an adhesive film is dissolved in asolvent to de-bond off the semiconductor circuit formation substrate.When the polyimide resin is used for the polyimide copolymer, thepolyimide mixed resin, or the (a) resin, a rework solvent describedlater is preferably used for a solvent to be used for the solventrelease method.

The manufacturing method of the present invention may include a step ofreworking an adhesive layer or a residue of an adhesive layerrespectively remaining on the semiconductor circuit formation substrateor the support substrate with an organic solvent, an alkaline aqueoussolution or the like after the step of de-bonding off the semiconductorcircuit formation substrate from the support substrate.

When the polyimide resin is used for the polyimide copolymer, thepolyimide mixed resin, or the (a) resin, it is preferred to use a reworksolvent containing (A) an amine-based solvent and (B) a solventrepresented by the general formula (6) as the rework solvent:

in which R²⁵ and R²⁶ independently represent hydrogen, alkyl groupshaving 1 to 12 carbon atoms, an acetyl group, or aromatic groups, R²⁷represents hydrogen or a methyl group, b is either 0, 1 or 2, and c isan integer of 1 to 3.

The (A) amine-based solvent has the effect of ring-opening an imidegroup to make it easily dissolve in the rework solvent, and therefore awashing time can be shortened. Amine-based solvents including primaryamines and secondary amines are preferred for ring-opening the imidegroup, and specific examples thereof include, but not limited to,monomethanolamine, dimethanolamine, monoethanolamine, dimethanolamine,dimethylamine, monopropanolamine, isopropanolamine, isopropylamine,diisopropylamine and the like. More preferred ones are amine-basedsolvents including primary amines, and specific examples thereofinclude, but not limited to, monomethanolamine, monoethanolamine,monopropanolamine, isopropanolamine, isopropylamine and the like.

From the viewpoint of solubility of the polyimide copolymer, thepolyimide mixed resin or the polyimide resin, the rework solventpreferably contains the solvent represented by the general formula (6),and specific examples of such solvents include, but not limited to,propylene glycol mono-t-butyl ether, ethylene glycol mono-t-butyl ether,propylene glycol mono-n-butyl ether, propylene glycol monopropyl ether,propylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether,ethylene glycol monopropyl ether, dipropylene glycol dimethyl ether,dipropylene glycol diethyl ether, dipropylene glycol dipropyl ether,dipropylene glycol di-n-butyl ether, dipropylene glycol di-t-butylether, dipropylene glycol monomethyl ether, dipropylene glycol monoethylether, dipropylene glycol monopropyl ether, dipropylene glycolmono-n-butyl ether, tripropylene glycol monomethyl ether, tripropyleneglycol monoethyl ether, tripropylene glycol monopropyl ether, diethyleneglycol methyl ethyl ether, and diethylene glycol dimethyl ether.

Further, solvents which are represented by the general formula (6) andhave the SP value of 7.5 to 9.0, are more preferred. Examples of suchsolvents include dipropylene glycol dimethyl ether (SP value; 7.8),dipropylene glycol methyl-n-propyl ether (SP value; 8.0), diethyleneglycol methyl ethyl ether (SP value; 8.2), diethylene glycol dimethylether (SP value; 8.1), and the like. Dipropylene glycol dimethyl ether(SP value; 7.8) and dipropylene glycol methyl-n-propyl ether (SP value;8.0), in which the SP values are 7.5 to 8.0, are more preferred.

The rework solvent used in the present invention preferably contains anamide-based polar solvent in addition to the (A) and the (B). Theamide-based polar solvent has the effect of bringing the (A) and the (B)into a compatibly mixed state and improving the storage stability of therework solvent. Polar solvents including a tertiary amide havingexcellent storage stability are preferred for the amide-based polarsolvent. Specific examples of the polar solvents include, but notlimited to, N-methyl-2-pyrrolidone, N,N-dimethylacetamide,N,N-dimethylformamide, 1,3-dimethyl-2-imidazoline and the like.

Further, the rework solvent may contain an aqueous solution of sodiumhydroxide, sodium hydrogen carbonate, potassium hydroxide ortetramethylammonium hydroxide, or an organic solvent such asdimethylsulfoxide, as required.

The rework solvent can be suitably used as a solvent to be used in thesolvent release-method at room temperature.

EXAMPLES

The present invention will be described below by way of examples. Thepresent invention is not limited to these examples. Evaluation methodsof measurement of glass transition temperature, measurement of 1% weightloss temperature, storage stability, adhesiveness evaluation, heatresistance evaluation, backgrinding evaluation, de-bonding evaluation,rework evaluation, and sedimentation evaluation of inorganic particles,will be described.

(1) Measurement of Glass Transition Temperature

Polyamic acid resin solutions described in the following SynthesisExamples 1 and 26 to 32 (PA1, PA26 to PA32) was applied onto a glosssurface of an electrolytic copper foil of 18 μm in thickness so as to be20 μm in thickness using a bar coater, and then the solution was driedat 80° C. for 10 minutes and at 150° C. for 10 minutes and furtherheat-treated at 250° C. for 10 minutes in a nitrogen atmosphere to beconverted to a polyimide, and thereby a polyimide-laminated copper foilwas obtained. Then, the whole area of the copper foil of the obtainedpolyimide-laminated copper foil was etched with a ferric chloridesolution to obtain a single film of polyimide.

About 10 mg of the obtained single film of polyimide was packed in analuminum standard container and measured using a differential scanningcalorimeter DSC-50 (manufactured by Shimadzu Corporation) (DSC method),and a glass transition temperature was calculated from an inflectionpoint of the resulting DSC curve. After the single film waspreliminarily dried at 80° C. for 1 hour, measurement was performed at atemperature raising rate of 20° C./min.

(2) Measurement of 1% Weight Loss Temperature

About 15 mg of the single film of polyimide obtained in the abovedescription was packed in an aluminum standard container and measuredusing a thermogravimetric analyzer TGA-50 (manufactured by ShimadzuCorporation). With respect to measuring conditions, the single film washeld at 60° C. for 30 minutes, and then a temperature of the single filmwas raised at a temperature raising rate of 5° C./min to 500° C.

From the resulting weight Loss curve, a temperature at which a weight ofthe single film was decreased by 1% was read, and this temperature wasdefined as a 1% weight Loss temperature.

(3) Storage Stability

The polyamic acid resin solution obtained in each Production Example wasstored at 23° C., and a separating property of the solution was visuallyobserved. Rating criteria are as follows.

S: Separation does not occur during storage of two weeks or more

A: Separation occurs during 1 to 2 weeks

B: Separation occurs within 1 week

C: Separation occurs within 3 days

(4) Adhesiveness Evaluation

The polyamic acid resin solution obtained in each Production Example wasapplied onto a 8-inch silicon wafer of 750 μm in thickness (manufacturedby Shin-Etsu Chemical Co., Ltd.) with a spin coater the number ofrevolutions of which was adjusted so that the applied polyamic acidresin solution has a thickness of 20 μm after drying and imidization,and the polyamic acid resin solution was heat-treated at 120° C. for 10minutes to be dried, and heat-treated at 350° C. for 1 hour to becompletely imidized, and thereby an adhesive layer-laminated siliconsubstrate was obtained.

On the adhesive layer-laminated silicon substrate prepared in the aboveway, a 8-inch alkali-free glass substrate of 0.7 mm in thickness(manufactured by Corning Incorporated) was overlaid, and waspress-bonded for 5 minutes at a load of 2000 N using a hot press machinewhose upper plate and lower plate were set at 180° C. to obtain a glasssubstrate-laminated silicon substrate.

In this case, when the glass substrate could be laminated on the siliconsubstrate, the adhesiveness was rated as “A”, and when the glasssubstrate could not be laminated, the adhesiveness was rated as “C”.

Further, the obtained glass substrate-laminated silicon substrate wasvisually observed from a glass side to evaluate the presence or absenceof voids. Rating criteria are as follows.

A: Void is not present

B: Voids of 1 cm or less are present

C: Voids of 1 cm or more are present

(5) Heat Resistances Evaluation

The glass substrate-laminated silicon substrate which was evaluated onthe adhesiveness in the above description was heat-treated at 350° C.for 2 hours and then was visually observed from a glass side to evaluatethe presence or absence of voids. Rating criteria are as follows.

A: Void is not present

B: Voids of 1 cm or less are present

C: Voids of 1 cm or more are present

(6) Evaluation of Backgrinding of Silicon Substrate

The glass substrate-laminated silicon substrate which was evaluated onthe heat resistance in the above description was set on a grinder DAG810(manufactured by DISCO Corporation), and a silicon substrate waspolished to a thickness of 100 μm. The silicon substrate after grindingwas visually observed to evaluate the presence or absence of fracturesor cracks.

(7) De-Bonding Evaluation

1. Mechanical De-Bonding Method at Room Temperature

A dicing tape was bonded to the silicon substrate of the glasssubstrate-laminated silicon substrate subjected to backgrinding in theabove description using a dicing frame, and the surface of the dicingtape was set on a suction pad by vacuum suction, and the glass substratewas de-bonded off at room temperature by lifting one point of the glasssubstrate with tweezers.

2. Solvent-De-Bonding Method at Room Temperature

Using a substrate obtained by providing the above-mentioned 8-inchalkali-free glass substrate with holes for a solvent passage, a glasssubstrate-laminated silicon substrate was prepared. Thereafter, theglass substrate-laminated silicon substrate was immersed in the reworksolvent obtained in Production Example 47 at 23° C. for 10 minutes, andthe substrate was de-bonded off with a hand.

Rating criteria of de-bonding evaluation are as follows.

A: Substrate can be de-bonded by both of 1. Mechanical de-bonding methodand 2. Solvent method.

B1: Substrate can be de-bonded only by 1. Mechanical de-bonding methodat room temperature.

B2: Substrate can be de-bonded only by 2. Solvent release method at roomtemperature.

C: Substrate can be de-bonded neither by 1. Mechanical de-bonding methodnor 2. Solvent release method.

(8) Rework Evaluation

The adhesive layer adhering to the silicon substrate de-bonded off inthe above description was reworked at 23° C. for 10 minutes with therework solvent obtained in Production Example 46, and a state ofsolubility of the adhesive layer was visually observed. Rating criteriaare as follows.

A: There is no residue of the adhesive layer

B: Adhesive layer is dissolved but a residue remains on the substrate

C: Adhesive layer is not dissolved

(9) Sedimentation Evaluation of Inorganic Particles

The polyamic acid resin solutions obtained in Production Examples 10 to45 were stored at 23° C., and the presence or absence of inorganicparticle sedimentation of each solution was visually observed. Ratingcriteria are as follows.

S: Sedimentation does not occur during storage of four weeks or more

A: Sedimentation occurs during 2 to 4 weeks

B: Sedimentation occurs within 2 weeks

C: Sedimentation occurs within 1 week

(10) Measurement of Average Molecular Weight and Calculation of Value ofn of Polysiloxane-Based Diamine

5 g of polysiloxane-based diamine serving as a specimen is taken and putinto a beaker, and to this, 50 ml of a mixed solution of IPA and toluenein proportions of 1:1 was added to dissolve the polysiloxane-baseddiamine therein. Next, using an automatic potentiometric titrator AT-610manufactured by Kyoto Electronics Manufacturing Co., Ltd., a 0.1 Naqueous hydrochloric acid solution was added dropwise while stirring thesolution, and an amount added dropwise at which the solution reaches aneutralization point was determined. An average molecular weight wascalculated from the resulting amount of the 0.1 N aqueous hydrochloricacid solution added dropwise using the following formula (7).

2×[10×36.5×(amount added dropwise(g))]/5=average molecular weight  (7)

Next, a molecular weight of the polysiloxane-based diamine used wascalculated from its chemical structural formula for the cases of n=1 andn=10, and thereby, a relationship between the value of n and themolecular weight was determined as a relational expression of a linearfunction. By applying the above average molecular weight to therelational expression, an average value of n was determined.

Names of abbreviations of acid dianhydrides, diamines, fillers andsolvents which are respectively shown in the following productionexamples, are as follows.

ODPA: 3,3′,4,4′-diphenyl ether tetracarboxylic dianhydridePMDA: pyromellitic dianhydrideBSAA: 4,4′-[(isopropylidene)bis(p-phenyleneoxy)]diphthalic dianhydrideSiDA: 1,1,3,3-tetramethyl-1,3-bis(3-aminopropyl)disiloxane (molecularweight: 248, n=1 in the formula (1))APPS1: α,ω-bis(3-aminopropyl)polydimethylsiloxane (average molecularweight: 400, n=3 in the formula (1))APPS2: α,ω-bis(3-aminopropyl)polydimethylsiloxane (average molecularweight: 860, n=9 in the formula (1))APPS3: α,ω-bis(3-aminopropyl)polydimethylsiloxane (average molecularweight: 1600, n=19 in the formula (1))APPS4: α,ω-bis(3-aminopropyl)polydimethylsiloxane (average molecularweight: 3000, n=37 in the formula (1))APPS5: α,ω-bis(3-aminopropyl)polydimethylsiloxane (average molecularweight: 4400, n=57 in the formula (1))44DAE: 4,4′-diaminodiphenyletherAPB: 1,3-bis(3-aminophenoxy)benzeneDABS: 4,4′-dihydroxy-3,3′-diaminophenyl sulfoneFDA: 9,9-bis(3-amino-4-hydroxyphenyl)fluoreneBAHF: 4,4′-dihydroxy-3,3′-diaminophenyl hexafluoropropaneMEK-ST-40: organic solvent-dispersed silica (solvent: MEK, silica: 40 wt%) (manufactured by NISSAN CHEMICAL INDUSTRIES, LTD.)DMM: Dipropylene glycol dimethyl etherDPMNP: Dipropylene glycol methyl-n-propyl etherEDM: Diethylene glycol methyl ethyl etherDPM: Dipropylene glycol methyl etherKBM-1003: Vinylsilane (manufactured by Shin-Etsu Chemical Co., Ltd.)

Synthesis Example 1 (Polymerization of Polyamic Acid)

Into a reaction oven equipped with a thermometer, a dry nitrogen inletport, a heating/cooling unit by warm water/cooling water and a stirringunit, 602.0 g (0.7 mol) of APPS2 and 60.1 g (0.3 mol) of 44DAE werecharged together with 972.3 g of DMM, and the resulting mixture wasdissolved. To this, 310.2 g (1 mol) of ODPA was added, and the resultingmixture was reacted at room temperature for 1 hour and subsequently at60° C. for 5 hours to obtain a 50 wt % polyamic acid solution PAL Theglass transition temperature and 1% weight Loss temperature of theobtained polyamic acid were measured and summarized in Table 4.

Synthesis Examples 2 to 32 (Polymerization of Polyamic Acid)

50 wt % polyamic acid solutions (PA2 to PA32) were obtained by the sameoperation as in Production Example 1 except for changing types andcharged amounts of the acid dianhydride and diamine as shown in Tables 1to 4. The glass transition temperature and 1% weight Loss temperature ofeach of the obtained polyamic acids of PA26 to PA32 were measured andsummarized in Table 4.

TABLE 1 Upper line: composition ratio (mol %)/lower line: charged amount(g) Resin concentration; 50 wt % Diamine Solvent (g) Acid Dianhydride(A1) (B1) Aromatic DMM ODPA APPS1 APPS2 APPS3 APPS4 APPS5 44DAE (SPvalue; 7.8) Synthesis PA1 100 70 30 972.3 Example 1 310.2 602.0 60.1Synthesis PA2 100 30 10 60 1128.3 Example 2 310.2 258 440.0 120.1Synthesis PA3 100 50 10 40 1260.3 Example 3 310.2 430.0 440.0 80.1Synthesis PA4 100 70 10 20 915.1 Example 4 155.1 280.0 440 40.0Synthesis PA5 100 70 10 20 1422.4 Example 5 620.4 602.0 160 40.0Synthesis PA6 100 70 10 20 1562.4 Example 6 620.4 602.0 300.0 40.0Synthesis PA7 100 70 10 20 1392.2 Example 7 310.2 602.0 440 40.0Synthesis PA8 100 70 0.01 29.99 972.7 Example 8 310.2 602.0 0.44 60.04Synthesis PA9 100 70 0.1 29.9 976.5 Example 9 310.2 602.0 4.4 59.9Synthesis PA10 100 70 1 29 1014.3 Example 10 310.2 602.0 44 58.1Synthesis PA11 100 60 30 10 2166.2 Example 11 310.2 516.0 1320 20.0Synthesis PA12 100 40 50 10 2874.2 Example 12 310.2 344.0 2200 20.0

TABLE 2 Upper line: composition ratio (mol %)/lower line: charged amount(g) Resin concentration; 50 wt % Diamine Acid Dianhydride (A1) (B1)Aromatic ODPA PMDA BSAA APPS2 APPS5 44DAE APB DABS Synthesis PA13 100 3070 Example 13 310.2 344.0 3080 Synthesis PA14 100 70 10 20 Example 14310.2 602.0 440 58.5 Synthesis PA15 100 70 10 20 Example 15 310.2 602.0440 49.7 Synthesis PA16 100 70 10 20 Example 16 218.1 602.0 440 40.0Synthesis PA17 100 70 10 20 Example 17 520.5 602.0 440 40.0 SynthesisPA18 100 70 10 20 Example 18 310.2 602.0 440 40.0 Synthesis PA19 100 7010 20 Example 19 310.2 602.0 440 40.0 Synthesis PA20 100 70 10 20Example 20 310.2 602.0 440 40.0 Synthesis PA21 100 40 50 Example 21310.2 344.0 2200 Synthesis PA22 100 40 50 Example 22 310.2 344.0 2200Solvent (g) Diamine DMM DPMNP EDM DPM Aromatic (SP value; (SP value; (SPvalue; (SP value; FDA BAHF 7.8) 8.0) 8.2) 9.7) Synthesis PA13 3734.2Example 13 Synthesis PA14 1410.7 Example 14 Synthesis PA15 1401.9Example 15 Synthesis PA16 1300.1 Example 16 Synthesis PA17 1602.5Example 17 Synthesis PA18 1392.24 Example 18 Synthesis PA19 1392.24Example 19 Synthesis PA20 1392.24 Example 20 Synthesis PA21 10 2893.6Example 21 39.4 Synthesis PA22 10 2890.8 Example 22 36.6

TABLE 3 Upper line: composition ratio (mol %)/lower line: charged amount(g) resin concentration; 50 wt % Diamine Solvent (g) Acid Dianhydride(A2) (B2) Aromatic DMM ODPA APPS1 APPS4 APPS5 44DAE (SP value; 7.8)Synthesis PA23 100 70 30 650.26 Example 23 310.2 280 60.1 Synthesis PA24100 70 30 2470.26 Example 24 310.2 2100.0 60.1 Synthesis PA25 100 70 303450.26 Example 25 310.2 3080.0 60.1

TABLE 4 Upper line: ratio (mol %)/lower line: content (g) Resinconcentration; 50 wt % Diamine Solvent (g) 1% Weight Loss AcidDianhydride Siloxane-based Aromatic DMM Tg Temperature ODPA SiDA APPS2APPS3 44DAE APB FDA BAHF (SP value; 7.8) (° C.) (° C.) Synthesis PA1 10070 30 972.3 30 367 Example 1 310.2 602.0 60.1 Synthesis PA26 100 70 301490.3 19 364.0 Example 26 310.2 1120.0 60.1 Synthesis PA27 100 30 70930.4 130 411.0 Example 27 310.2 480.0 140.2 Synthesis PA28 100 40 601070.4 88 402 Example 28 310.2 640.0 120.2 Synthesis PA29 100 70 30999.9 16 371 Example 29 310.2 602.0 87.7 Synthesis PA30 100 80 20 548.6112 392 Example 30 310.2 198.4 40.0 Synthesis PA31 100 75 10 15 1043.665 391 Example 31 310.2 645.0 29.3 59.1 Synthesis PA32 100 75 10 151039.4 40 371 Example 32 310.2 645.0 29.3 54.9

Synthesis Example 33 (Synthesis of (b-1) Siloxane Compound)

Into a reaction oven equipped with a thermometer, a dry nitrogen inletport, a heating/cooling unit by warm water/cooling water and a stirringunit, 1600.0 g (1.0 mol) of APPS3 was charged together with 1896.2 g ofDMM, and the resulting mixture was dissolved. To this, 296.2 g (2.0 mol)of phthalic anhydride was added, and the resulting mixture was reactedat room temperature for 1 hour and subsequently at 60° C. for 5 hours toobtain a 50 wt % siloxane compound solution ((b-1)-1).

Synthesis Examples 34, 35 (Synthesis of (b-1) Siloxane Compound)

50 wt % siloxane compound solutions ((b-1)-2, (b-1)-3) were obtained bythe same operation as in Production Example 1 except for changing typesand charged amounts of the siloxane diamine and phthalic anhydride-basedcompound as shown in Table 5.

TABLE 5 Upper line: ratio (mol %)/lower line: content (g) Concentration:50 wt % Terminal Solvent Siloxane Diamine Phthalic 4-tert-ButylphthalicDMM APPS3 APPS5 Anhydride Anhydride (SP value; 7.8) Synthesis (b-1)-1100 200 1896.2 Example 33 1600.0 296.2 Synthesis (b-1)-2 100 200 4808.4Example 34 4400 408.4 Synthesis (b-1)-3 100 200 4696.2 Example 35 4400.0296.2

Synthesis Example 36

Into a 500 ml flask, 500 g of hexane was put, and to this, 21.33 g (0.1mol) of aminophenyltrimethoxysilane (3-aminophenyltrimethoxysilane and4-aminophenyltrimethoxysilane are mixed in a weight ratio of 6:4) wasadded. Subsequently, 10.21 g (0.1 mol) of an acetic anhydride was addeddropwise slowly, and the resulting mixture was reacted at roomtemperature for 3 hours. A sediment was separated by filtration anddried, and the resulting synthesized product was referred to as AcAPMS.A structure of the AcAPMS is shown below.

Production Example 1 (Preparation of Adhesive Resin Composition)

Into a reaction oven equipped with a stirring unit, 99.99 g of thepolyamic acid solution (PA1) obtained in Synthesis Example 1 and 0.01 gof the polyamic acid solution (PA25) obtained in Synthesis Example 25were charged, and the resulting mixture was stirred at room temperaturefor 2 hours to obtain an adhesive resin composition (PB1).

Production Examples 2 to 9 (Preparation of Adhesive Resin Composition)

Adhesive resin compositions (PB2 to PB9) were obtained by the sameoperation as in Production Example 1 except for changing types andcharged amounts of the polyamic acid solution as shown in Table 6.

TABLE 6 Polyamic Acid Solution (A2) Polyamic Acid Solution (B2) n inGeneral Charged n in General Charged Type Formula (1) Amount (g) TypeFormula (1) Amount (g) Production PB1 PA1 9 99.99 PA25 57 0.01 Example 1Production PB2 PA1 9 99.9 PA25 57 0.1 Example 2 Production PB3 PA1 9 99PA25 57 1 Example 3 Production PB4 PA1 9 90 PA25 57 10 Example 4Production PB5 PA1 9 70 PA25 57 30 Example 5 Production PB6 PA1 9 50PA25 57 50 Example 6 Production PB7 PA1 9 30 PA25 57 70 Example 7Production PB8 PA1 9 90 PA24 37 10 Example 8 Production PB9 PA23 3 90PA25 57 10 Example 9

Production Example 10 (Preparation of Adhesive Resin Composition)

Into a reaction oven equipped with a stirring unit, 100 g of thepolyamic acid solution (PA12) obtained in Synthesis Example 12 and 1.25g of MEK-ST-40 as a filler solution were charged, and the resultingmixture was stirred at room temperature for 2 hours to obtain anadhesive resin composition (AH1).

Production Examples 11 to 14 (Preparation of Adhesive Resin Composition)

Adhesive resin compositions (AH2 to AH5) were obtained by the sameoperation as in Production Example 10 except for changing types andcharged amounts of the polyamic acid solution as shown in Table 7.

TABLE 7 Polyamic Acid Solution Filler Charged Charged Weight Ratio TypeAmount (g) Type Amount (g) to Resin Production AH1 PA12 100 MEK-ST-401.25  1% Example 10 Production AH2 PA12 100 MEK-ST-40 6.25  5% Example11 Production AH3 PA12 100 MEK-ST-40 12.5 10% Example 12 Production AH4PA21 100 MEK-ST-40 18.8 15% Example 13 Production AH5 PA22 100 MEK-ST-4018.8 15% Example 14

Production Example 15 (Preparation of Adhesive Resin Composition)

Into a reaction oven equipped with a stirring unit, 200.0 g of thepolyamic acid solution (PA1) obtained in Synthesis Example 1, 10.0 g ofa 50 wt % APPS5 solution (solvent: DMM), 5.0 g of AcAPMS obtained inSynthesis Example 33, and 12.0 g of MEK-ST-40 as a filler solution werecharged, and the resulting mixture was stirred at room temperature for 2hours to obtain an adhesive resin composition (AH6).

Production Examples 16 to 45 (Preparation of Adhesive Resin Composition)

Adhesive resin compositions (AH7 to AH36) were obtained by the sameoperation as in Production Example 15 except for changing chargedamounts of the (a) resin, the (b-1) compound of the general formula (2),the (b-2) compound of the general formula (3) and the MEK-ST-40 as shownin Table 8.

TABLE 8 (b-1) Compound of General (a) Resin Formula (1) (b-2) Compoundof General Inorganic Particle concentration: 50 wt % Concentration: 50wt % Formula (2) concentration: 40 wt % Charged Charged Charged ChargedType Amount (g) Type Amount (g) Type Amount (g) Type Amount (g)Production AH6 PA1 200.0 APPS5 10.0 AcAPMS 5.0 MEK-ST-40 12.0 Example 15Production AH7 PA24 200.0 APPS5 10.0 AcAPMS 5.0 MEK-ST-40 12.0 Example16 Production AH8 PA25 200.0 APPS5 10.0 AcAPMS 5.0 MEK-ST-40 12.0Example 17 Production AH9 PA26 200.0 APPS5 10.0 AcAPMS 5.0 MEK-ST-4012.0 Example 18 Production AH10 PA27 200.0 APPS5 10.0 AcAPMS 5.0MEK-ST-40 12.0 Example 19 Production AH11 PA28 200.0 APPS5 10.0 AcAPMS5.0 MEK-ST-40 12.0 Example 20 Production AH12 PA1 200.0 (b-1)-1 10.0AcAPMS 5.0 MEK-ST-40 12.0 Example 21 Production AH13 PA1 200.0 (b-1)-210.0 AcAPMS 5.0 MEK-ST-40 12.0 Example 22 Production AH14 PA1 200.0(b-1)-3 10.0 AcAPMS 5.0 MEK-ST-40 12.0 Example 23 Production AH15 PA1200.0 APPS3 10.0 AcAPMS 5.0 MEK-ST-40 12.0 Example 24 Production AH16PA1 200.0 APPS5 0.02 AcAPMS 5.0 MEK-ST-40 12.0 Example 25 ProductionAH17 PA1 200.0 APPS5 0.2 AcAPMS 5.0 MEK-ST-40 12.0 Example 26 ProductionAH18 PA1 200.0 APPS5 2.0 AcAPMS 5.0 MEK-ST-40 12.0 Example 27 ProductionAH19 PA1 200.0 APPS5 20.0 AcAPMS 5.0 MEK-ST-40 12.0 Example 28Production AH20 PA1 200.0 APPS5 40.0 AcAPMS 5.0 MEK-ST-40 12.0 Example29 Production AH21 PA1 200.0 APPS5 60.0 AcAPMS 5.0 MEK-ST-40 12.0Example 30 Production AH22 PA1 200.0 APPS5 10.0 AcAPMS 0.01 MEK-ST-4012.0 Example 31 Production AH23 PA1 200.0 APPS5 10.0 AcAPMS 0.1MEK-ST-40 12.0 Example 32 Production AH24 PA1 200.0 APPS5 10.0 AcAPMS1.0 MEK-ST-40 12.0 Example 33 Production AH25 PA1 200.0 APPS5 10.0AcAPMS 10.0 MEK-ST-40 12.0 Example 34 Production AH26 PA1 200.0 APPS510.0 AcAPMS 20.0 MEK-ST-40 12.0 Example 35 Production AH27 PA1 200.0APPS5 10.0 AcAPMS 30.0 MEK-ST-40 12.0 Example 36 Production AH28 PA1200.0 APPS5 10.0 MEK-ST-40 12.0 Example 37 Production AH29 PA1 200.0(b-1)-3 10.0 MEK-ST-40 12.0 Example 38 Production AH30 PA1 200.0 AcAPMS5.0 MEK-ST-40 12.0 Example 39 Production AH31 PA1 200.0 MEK-ST-40 12.0Example 40 Production AH32 PA1 200.0 APPS2 10.0 MEK-ST-40 12.0 Example41 Production AH33 PA1 200.0 KBM-1003 10.0 MEK-ST-40 12.0 Example 42Production AH34 PA29 200.0 APPS5 10.0 AcAPMS 5.0 MEK-ST-40 12.0 Example43 Production AH35 PA30 200.0 APPS5 10.0 AcAPMS 5.0 MEK-ST-40 75.0Example 44 Production AH36 PA29 200.0 APPS5 10.0 AcAPMS 5.0 MEK-ST-4075.0 Example 45

Production Example 46 (Preparation of Rework Solvent)

Into a reaction oven equipped with a stirring unit, 30 g ofmonoethanolamine, 30 g of DMM, and 30 g of N-methyl-2-pyrrolidone werecharged, and the resulting mixture was stirred at room temperature for 1hour to obtain a rework solvent.

Example 1

The polyamic acid solution (PA3) obtained in Synthesis Example 3 wasapplied onto a 8-inch silicon substrate of 750 mm in thickness(manufactured by Shin-Etsu Chemical Co., Ltd.) with a spin coater thenumber of revolutions of which was adjusted so that the applied polyamicacid solution has a thickness of 20 μm after drying and imidization, andthe polyamic acid solution was heat-treated at 120° C. for 10 minutes tobe dried, and heat-treated at 350° C. for 1 hour to be completelyimidized, and thereby an adhesive layer-laminated silicon substrate wasobtained.

On the adhesive layer-laminated silicon substrate prepared in the aboveway, a 8-inch alkali-free glass substrate of 0.7 mm in thickness(manufactured by Corning Incorporated) was overlaid, and waspress-bonded for 5 minutes at a load of 2000 N using a hot press machinewhose upper plate and lower plate were set at 180° C. to obtain a glasssubstrate-laminated silicon substrate. Using the obtained glasssubstrate-laminated silicon substrate, evaluations of adhesiveness, heatresistance, backgrinding of a silicon substrate, de-bonding and reworkwere performed, and results thereof are summarized in Table 9. Further,the storage stability of the polyamic acid resin composition wasevaluated, and the result thereof is summarized in Table 9.

Examples 2 to 25

Glass substrate-laminated silicon substrates were obtained by the sameoperation as in Example 1 except for changing the polyamic acid resincomposition to compositions shown in Table 9 and Table 10.

Using each of the obtained glass substrate-laminated silicon substrates,evaluations of adhesiveness, heat resistance, backgrinding of a siliconsubstrate, de-bonding and rework were performed, and results thereof aresummarized in Table 9 and Table 10. Further, the storage stability ofeach of the polyamic acid resin compositions was evaluated, and theresult thereof is summarized in Table 9 and Table 10.

Comparative Examples 1 to 3

Glass substrate-laminated silicon substrates were obtained by the sameoperation as in Example 1 except for changing the polyamic acid resincomposition to compositions shown in Table 8 and Table 9.

Using each of the obtained glass substrate-laminated silicon substrates,evaluations of adhesiveness, heat resistance, backgrinding of a siliconsubstrate, de-bonding and rework were performed, and results thereof aresummarized in Table 9 and Table 10. Further, the storage stability ofeach of the polyamic acid resin compositions was evaluated, and theresult thereof is summarized in Table 9 and Table 10.

TABLE 9 Temporary- (a1) (b1) Bonding n in General Content n in GeneralContent Storage Adhesive Formula (1) (mol %) Formula (1) (mol %) SolventStability Example 1 PA3 9 50 57 10 DMM S Example 2 PA4 3 70 57 10 DMM SExample 3 PA5 9 70 19 10 DMM S Example 4 PA6 9 70 37 10 DMM S Example 5PA7 9 70 57 10 DMM S Example 6 PA8 9 70 57 0.01 DMM S Example 7 PA9 9 7057 0.1 DMM S Example 8 PA10 9 70 57 1 DMM S Example 9 PA11 9 60 57 30DMM S Example 10 PA12 9 40 57 50 DMM S Example 11 PA14 9 70 57 10 DMM SExample 12 PA15 9 70 57 10 DMM S Example 13 PA16 9 70 57 10 DMM SExample 14 PA17 9 70 57 10 DMM S Example 15 PA18 9 70 57 10 DPNMP SExample 16 PA19 9 70 57 10 EDM A Example 17 PA20 9 70 57 10 DPM BComparative PA2 9 30 57 10 DMM S Example 1 Comparative PA13 9 30 57 70DMM S Example 2 Heat Resistances Adhesiveness Evaluation Evaluation VoidVoid Fractures after De-bonding Rework Adhesiveness EvaluationEvaluation Backgrinding Evaluation Evaluation Example 1 A A A none A AExample 2 A A A none A A Example 3 A A A none A A Example 4 A A A none AA Example 5 A A A none A A Example 6 A A A none A A Example 7 A A A noneA A Example 8 A A A none A A Example 9 A A A none A A Example 10 A A Bnone A A Example 11 A A A none A A Example 12 A A A none A A Example 13A A A none A A Example 14 A A A none A A Example 15 A A A none A AExample 16 A A A none A A Example 17 A A A none A A Comparative C notperformed because of defective adhesiveness Example 1 Comparative A A Cpresent B A Example 2

TABLE 10 Temporary- (a1) (b1) Bonding n in General Content n in GeneralContent Storage Adhesive Formula (1) (mol %) Formula (1) (mol %) SolventStability Example 18 PB1 9 99.99 57 0.01 DMM S Example 19 PB2 9 99.9 570.1 DMM S Example 20 PB3 9 99 57 1 DMM S Example 21 PB4 9 90 57 10 DMM SExample 22 PB5 9 70 57 30 DMM S Example 23 PB6 9 50 57 50 DMM S Example24 PB8 9 90 37 10 DMM S Example 25 PB9 3 90 57 10 DMM S Comparative PB79 30 57 70 DMM S Example 3 Heat Resistances Adhesiveness EvaluationEvaluation Void Void Fractures after De-bonding Rework AdhesivenessEvaluation Evaluation Backgrinding Evaluation Evaluation Example 18 A AA none A A Example 19 A A A none A A Example 20 A A A none A A Example21 A A A none A A Example 22 A A A none A A Example 23 A A B none A AExample 24 A A A none A A Example 25 A A A none A A Comparative A A Cpresent B A Example 3

Examples 26 to 58

Glass substrate-laminated silicon substrates were obtained by the sameoperation as in Example 1 except for changing the polyamic acid resincomposition to compositions shown in Table 11 to Table 13.

Using each of the obtained glass substrate-laminated silicon substrates,evaluations of adhesiveness, heat resistance, backgrinding of a siliconsubstrate, de-bonding and rework were performed, and results thereof aresummarized in Table 11 to Table 13. Further, the storage stability ofeach of the polyamic acid resin compositions was evaluated and thesedimentation evaluation of inorganic particles was performed, and theresults thereof are summarized in Table 11 to Table 13.

Comparative Examples 4 to 6

Glass substrate-laminated silicon substrates were obtained by the sameoperation as in Example 1 except for changing the polyamic acid resincomposition to compositions shown in Table 11 to Table 13.

Using each of the obtained glass substrate-laminated silicon substrates,evaluations of adhesiveness, heat resistance, backgrinding of a siliconsubstrate, de-bonding and rework were performed, and results thereof aresummarized in Table 11 to Table 13. Further, the storage stability ofeach of the polyamic acid resin compositions was evaluated and thesedimentation evaluation of inorganic particles was performed, and theresults thereof are summarized in Table 11 to Table 13.

TABLE 11 Temporary- (a1) (b1) Weight Ratio to Adhesiveness EvaluationBonding n in General Content n in General Content Inorganic Storage VoidAdhesive Formula (1) (mol %) Formula (1) (mol %) Particle ResinStability Adhesiveness Evaluation Example 26 AH1 9 40 57 50  1% S A AExample 27 AH2 9 40 57 50  5% S A A Example 28 AH3 9 40 57 50 10% S A AExample 29 AH4 9 40 57 50 15% S A A Example 30 AH5 9 40 57 50 15% S A AHeat Resistances Evaluation Sedimentation Void Fractures afterDe-bonding Rework Evaluation of Evaluation Backgrinding EvaluationEvaluation Inorganic Particles Example 26 A none A A A Example 27 A noneA A A Example 28 A none A A A Example 29 A none A A S Example 30 A noneA A S

TABLE 12 (a) Resin (b-1) Temporary- 1% Weight Loss n in Addition RatioBonding Tg Temperature General to (a) Resin Adhesive Type (° C.) (° C.)Type Formula (1) (wt %) Example 31 AH6 PA1 30 367 APPS5 57 5 Example 32AH7 PA26 19 364 APPS5 57 5 Example 33 AH8 PA27 130 411 APPS5 57 5Example 34 AH9 PA28 88 402 APPS5 57 5 Example 35 AH10 PA29 16 371 APPS557 5 Example 36 AH11 PA30 112 392 APPS5 57 5 Example 37 AH12 PA1 30 367(b-1)-1 19 5 Example 38 AH13 PA1 30 367 (b-1)-2 57 5 Example 39 AH14 PA130 367 (b-1)-3 57 5 Example 40 AH15 PA1 30 367 APPS3 57 5 Example 41AH16 PA1 30 367 APPS5 57 0.01 Example 42 AH17 PA1 30 367 APPS5 57 0.1Example 43 AH18 PA1 30 367 APPS5 57 1 Example 44 AH19 PA1 30 367 APPS557 10 Example 45 AH20 PA1 30 367 APPS5 57 20 Example 46 AH21 PA1 30 367APPS5 57 30 Example 47 AH22 PA1 30 367 APPS5 57 5 Example 48 AH23 PA1 30367 APPS5 57 5 Example 49 AH24 PA1 30 367 APPS5 57 5 Example 50 AH25 PA130 367 APPS5 57 5 Example 51 AH26 PA1 30 367 APPS5 57 5 Example 52 AH27PA1 30 367 APPS5 57 5 Example 53 AH28 PA1 30 367 APPS5 57 5 Example 54AH29 PA1 30 367 (b-1)-3 57 5 Example 55 AH30 PA1 30 367 without additionExample 56 AH34 PA31 65 391 APPS5 57 5 Example 57 AH35 PA32 40 371 APPS557 5 Example 58 AH36 PA31 65 391 APPS5 57 5 Comparative AH31 PA1 30 367without addition Example 4 Comparative AH32 PA1 30 367 APPS2 9 5.0Example 5 Comparative AH33 PA1 30 367 without addition Example 6 (b-2)Addition Ratio Weight Ratio to to (a) Resin Inorganic Particle Type (wt%) Resin Solvent Example 31 AcAPMS 5 4.80% DMM Example 32 AcAPMS 5 4.80%DMM Example 33 AcAPMS 5 4.80% DMM Example 34 AcAPMS 5 4.80% DMM Example35 AcAPMS 5 4.80% DMM Example 36 AcAPMS 5 4.80% DMM Example 37 AcAPMS 54.80% DMM Example 38 AcAPMS 5 4.80% DMM Example 39 AcAPMS 5 4.80% DMMExample 40 AcAPMS 5 4.80% DMM Example 41 AcAPMS 5 4.80% DMM Example 42AcAPMS 5 4.80% DMM Example 43 AcAPMS 5 4.80% DMM Example 44 AcAPMS 54.80% DMM Example 45 AcAPMS 5 4.80% DMM Example 46 AcAPMS 5 4.80% DMMExample 47 AcAPMS 0.01 4.80% DMM Example 48 AcAPMS 0.1 4.80% DMM Example49 AcAPMS 1 4.80% DMM Example 50 AcAPMS 10 4.80% DMM Example 51 AcAPMS20 4.80% DMM Example 52 AcAPMS 30 4.80% DMM Example 53 without addition4.80% DMM Example 54 without addition 4.80% DMM Example 55 AcAPMS 54.80% DMM Example 56 AcAPMS 5 4.80% DMM Example 57 AcAPMS 5 15.00% DMMExample 58 AcAPMS 5 15.00% DMM Comparative without addition 4.80% DMMExample 4 Comparative without addition 4.80% DMM Example 5 ComparativeKBM-1003 5.0 4.80% DMM Example 6

TABLE 13 Heat Resistances Temporary- Adhesiveness Evaluation EvaluationSedimentation Bonding Storage Void Void Fractures after De-bondingRework Evaluation of Adhesive Stability Adhesiveness EvaluationEvaluation Backgrinding Evaluation Evaluation Inorganic ParticlesExample 31 AH6 S A A A none A A A Example 32 AH7 S A A A none A A AExample 33 AH8 S A B A none A A A Example 34 AH9 S A A A none A A AExample 35 AH10 S A A A none A A A Example 36 AH11 S A B A none A A AExample 37 AH12 S A A A none A A A Example 38 AH13 S A A A none A A AExample 39 AH14 S A A A none A A A Example 40 AH15 S A A A none A A AExample 41 AH16 S A A A none A A A Example 42 AH17 S A A A none A A AExample 43 AH18 S A A A none A A A Example 44 AH19 S A A A none A A AExample 45 AH20 S A B A none A A A Example 46 AH21 S A B A none A A AExample 47 AH22 S A A A none A A A Example 48 AH23 S A A A none A A AExample 49 AH24 S A A A none A A A Example 50 AH25 S A A A none A A AExample 51 AH26 S A A B none A A A Example 52 AH27 S A A B none A A AExample 53 AH28 S A A B none A A A Example 54 AH29 S A A A none A A AExample 55 AH30 S A A A none B2 A A Example 56 AH34 S A A A none A A SExample 57 AH35 S A A A none A A S Example 58 AH36 S A A A none A A SComparative AH31 S A A C present B2 A A Example 4 Comparative AH32 S A AC present B2 A A Example 5 Comparative AH33 S A A C present B2 A AExample 6

1. A temporary-bonding adhesive, wherein the temporary-bonding adhesiveis a polyimide copolymer having at least an acid dianhydride residue anda diamine residue, the diamine residue includes both of (A1) apolysiloxane-based diamine residue represented by a general formula (1)in which n is a natural number of 1 to 15, and (B1) a polysiloxane-baseddiamine residue represented by a general formula (1) in which n is anatural number of 16 to 100, and the polyimide copolymer contains 40 to99.99 mol % of the (A1) residue and 0.01 to 60 mol % of the (B1)residue:

in which n is a natural number, R¹ and R² may be the same or differentand represent an alkylene group having 1 to 30 carbon atoms or aphenylene group, and R³ to R⁶ may be the same or different and representan alkyl group having 1 to 30 carbon atoms, a phenyl group, or a phenoxygroup.
 2. A temporary-bonding adhesive, wherein the temporary-bondingadhesive is a polyimide mixed resin including (A2) a polyimide and/or aprecursor thereof having at least an acid dianhydride residue and adiamine residue, containing a polysiloxane-based diamine residuerepresented by a general formula (1) in which n is a natural number of 1to 15 and not containing a polysiloxane-based diamine residuerepresented by a general formula (1) in which n is a natural number of16 to 100, and (B2) a polyimide and/or a precursor thereof having atleast an acid dianhydride residue and a diamine residue, containing apolysiloxane-based diamine residue represented by a general formula (1)in which n is a natural number of 16 to 100 and not containing apolysiloxane-based diamine residue represented by a general formula (1)in which n is a natural number of 1 to 15, and the polyimide mixed resincontains 40 to 99.99 wt % of the (A2) and 0.01 to 60 wt % of the (B2):

in which n is a natural number, R¹ and R² may be the same or differentand represent an alkylene group having 1 to 30 carbon atoms or aphenylene group, and R³ to R⁶ may be the same or different and representan alkyl group having 1 to 30 carbon atoms, a phenyl group, or a phenoxygroup.
 3. A temporary-bonding adhesive, wherein the temporary-bondingadhesive is a resin composition containing (a) a resin (excluding asiloxane polymer represented by a general formula (2)), and at least oneof (b-1) a siloxane polymer represented by a general formula (2) and(b-2) a compound represented by a general formula (3).

in which m is an integer of 10 to 100, R² and R⁸ may be the same ordifferent and represent a monovalent organic group having 1 to 30 carbonatoms and 0 to 3 nitrogen atoms. R⁹ and R¹⁰ may be the same or differentand represent an alkylene group having 1 to 30 carbon atoms or aphenylene group, and R¹¹ to R¹⁴ may be the same or different andrepresent an alkyl group having 1 to 30 carbon atoms, an alkylene grouphaving 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbonatoms, a phenyl group, or a phenoxy group.

in which R¹⁵ represents a monovalent organic group having 2 to 20 carbonatoms and 1 to 3 nitrogen atoms, R¹⁶ represents hydrogen, an alkyl grouphaving 1 to 20 carbon atoms, or an aromatic group, and a represents aninteger of 0 to
 4. 4. The temporary-bonding adhesive according to claim3, wherein a glass transition temperature of the (a) resin is 100° C. orlower.
 5. The temporary-bonding adhesive according to claim 3, wherein a1% weight Loss temperature of the (a) resin is 300° C. or higher.
 6. Thetemporary-bonding adhesive according to claim 3, wherein the (a) resinis a polyimide resin.
 7. The temporary-bonding adhesive according toclaim 3, containing the (b-1) siloxane polymer represented by a generalformula (2) in an amount of 0.01 to 30 wt % with respect to the (a)resin.
 8. The temporary-bonding adhesive according to claim 3,containing the (b-2) compound represented by a general formula (3) in anamount of 0.01 to 30 wt % with respect to the (a) resin.
 9. Thetemporary-bonding adhesive according to claim 1, further comprising (c)a solvent.
 10. The temporary-bonding adhesive according to claim 9,wherein the (c) solvent contains a solvent having an SP value of 7.5 to9.0.
 11. The temporary-bonding adhesive according to claim 9, whereinthe (c) solvent contains a solvent represented by a general formula (6):

in which R²⁵ and R²⁶ independently represent hydrogen, alkyl groupshaving 1 to 12 carbon atoms, an acetyl group, or aromatic groups, R²⁷represents hydrogen or a methyl group, b is either 0, 1 or 2, and c isan integer of 1 to
 3. 12. The temporary-bonding adhesive according toclaim 1, further comprising inorganic particles.
 13. An adhesive layerobtained by forming a coating of the temporary-bonding adhesiveaccording to claim
 1. 14. A wafer work piece formed by bonding asemiconductor circuit formation substrate to a support substrate with atleast the adhesive layer according to claim 13 interposed therebetween.15. A wafer work piece formed by bonding a semiconductor circuitformation substrate to a support substrate with the adhesive layeraccording to claim 13 interposed therebetween.
 16. A method formanufacturing a semiconductor device using the wafer work pieceaccording to claim 14 comprising at least any one of a step offabricating the semiconductor circuit formation substrate into a thinnerone, a step of subjecting the semiconductor circuit formation substrateof the wafer work piece to device processing, a step of de-bonding offthe semiconductor circuit formation substrate of the wafer work piecefrom a support substrate, and a step of washing, with a solvent, anadhesive layer adhering to the semiconductor circuit formation substratede-bonded off from the wafer work piece or the support substrate of thewafer work piece.
 17. A method for manufacturing a semiconductor device,wherein the step of fabricating the semiconductor circuit formationsubstrate into a thinner one according to claim 16 comprises a step offabricating a thickness of the semiconductor circuit formation substrateto at least 1 μm and at most 100 μm.
 18. A rework solvent for cleaningthe adhesive layer adhering to the de-bonded semiconductor circuitformation substrate or support substrate, wherein the rework solventcontains at least (A) an amine-based solvent and (B) a solventrepresented by the general formula (6):

in which R²⁵ and R²⁶ independently represent hydrogen, alkyl groupshaving 1 to 12 carbon atoms, an acetyl group, or aromatic groups, R²⁷represents hydrogen or a methyl group, b is either 0, 1 or 2, and c isan integer of 1 to
 3. 19. A polyimide copolymer having at least an aciddianhydride residue and a diamine residue, wherein the diamine residueincludes both of (A1) a polysiloxane-based diamine residue representedby a general formula (1) in which n is a natural number of 1 to 15, and(B1) a polysiloxane-based diamine residue represented by a generalformula (1) in which n is a natural number of 16 to 100, and thepolyimide copolymer contains 40 to 99.99 mol % of the (A1) residue and0.01 to 60 mol % of the (B1) residue:

in which n is a natural number, R¹ and R² may be the same or differentand represent an alkylene group having 1 to 30 carbon atoms or aphenylene group, and R³ to R⁶ may be the same or different and representan alkyl group having 1 to 30 carbon atoms, a phenyl group, or a phenoxygroup.
 20. A polyimide mixed resin including (A2) a polyimide and/or aprecursor thereof having at least an acid dianhydride residue and adiamine residue, containing a polysiloxane-based diamine residuerepresented by a general formula (1) in which n is a natural number of 1to 15 and not containing a polysiloxane-based diamine residuerepresented by a general formula (1) in which n is a natural number of16 to 100, and (B2) a polyimide and/or a precursor thereof having atleast an acid dianhydride residue and a diamine residue, containing apolysiloxane-based diamine residue represented by a general formula (1)in which n is a natural number of 16 to 100 and not containing apolysiloxane-based diamine residue represented by a general formula (1)in which n is a natural number of 1 to 15, and the polyimide mixed resincontains 40 to 99.99 wt % of the (A2) and 0.01 to 60 wt % of the (B2):

in which n is a natural number, R¹ and R² may be the same or differentand represent an alkylene group having 1 to 30 carbon atoms or aphenylene group, and R³ to R⁶ may be the same or different and representan alkyl group having 1 to 30 carbon atoms, a phenyl group, or a phenoxygroup.
 21. A resin composition containing (a) a resin (excluding asiloxane polymer represented by a general formula (2)), and at least oneof (b-1) a siloxane polymer represented by a general formula (2) and(b-2) a compound represented by a general formula (3), wherein the (a)resin is a polyimide resin having at least an acid dianhydride residueand a diamine residue and including, in the diamine residue, apolysiloxane-based diamine residue represented by a general formula (5)which is 40 mol % or more in all diamine residues.

in which m is an integer of 10 to 100, R⁷ and R⁸ may be the same ordifferent and represent a monovalent organic group having 1 to 30 carbonatoms and 0 to 3 nitrogen atoms, R⁹ and R′° may be the same or differentand represent an alkylene group having 1 to 30 carbon atoms or aphenylene group, and R¹¹ to R¹⁴ may be the same or different andrepresent an alkyl group having 1 to 30 carbon atoms, an alkylene grouphaving 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbonatoms, a phenyl group, or a phenoxy group,

in which R¹⁵ represents a monovalent organic group having 2 to 20 carbonatoms and 1 to 3 nitrogen atoms, R¹⁶ represents hydrogen, an alkyl grouphaving 1 to 20 carbon atoms, or an aromatic group, and a represents aninteger of 0 to 4,

in which L is an integer of 1 to 100, R¹⁹ and R²⁰ may be the same ordifferent and represent an alkylene group having 1 to 30 carbon atoms ora phenylene group, and R²¹ to R²⁴ may be the same or different andrepresent an alkyl group having 1 to 30 carbon atoms, a phenyl group, ora phenoxy group.